Racemoselective synthesis of ansa-metallocene compounds, ansa-metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers

ABSTRACT

A metallocene compound with the 4- and 7-positions on the indenyl moiety possessing large aromatic substituents is prepared in accordance with a method which produces substantially 100 percent racemic isomer. Advantageously, polymerization catalysts including the metallocene of the invention provide superior olefin polymerization results.

BACKGROUND

1. Field of the Invention

The present invention relates to a novel racemoselective synthesis ofansa-metallocene compounds, novel ansa-metallocene compounds useful ascomponents in polymerization catalysts, a process for the polymerizationof olefins, particularly propylene, and olefin homopolymers, random andimpact copolymers prepared by using the metallocene catalysts.

2. Background of the Art

Chiral ansa-metallocenes of transition metals of the groups three to sixof the Periodic Table of Elements are increasingly being used ascomponents for the stereospecific polymerization of olefins. Forexample, bridged substituted bis(indenyl) zirconium dichlorides areamong the most important class of catalyst components for themanufacturing of isotactic polypropylene [Brintzinger, H. H.; Fischer,D.; Mühlhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed.Engl. 1995, 34, 1143./Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F.Chem. Rev. 2000, 100, 1253/Pasquini, N. (Editor), PolypropyleneHandbook, 2^(nd) Ed. 2005, Carl-Hanser Verlag München]. Appropriatelysubstituted ansa-metallocene complexes for the generation of isotacticpolypropylene are generally obtained as mixtures of the racemic form andthe undesired meso form from the processes of the prior art.

The classical synthesis of ansa-metallocenes to the prior art generallyinvolves the deprotonation of a bis-indenyl-ligand by a strong base,followed by the reaction with zirconium tetrachloride or its solventadducts. This classical path has two substantial drawbacks. Instead ofthe desired racemate, almost equivalent amounts of the mirror-symmetricmeso diastereomer are formed in most cases. The meso isomer has to beremoved from the mixture, either by means of destruction of the mesoform, or removal by crystallization steps. The separation proceduregenerally lowers the yield of the amount of possible pure racemiccomplex. The other drawback is the low solubility of metallocenecomplexes, which leads to the use of large amounts of solvents for thefinal separation of the racemic and meso forms.

Several, so called “racemoselective” syntheses were described in theliterature [see LoCoco, M. D.; Zhang, X.; Jordan, R. F., J. Am. Chem.Soc. 2004; 126 (46); 15231-15244 and cited lit.], comprising the use ofalternative zirconium sources, which have to be synthesized prior to themanufacturing of the metallocene. WO2004/037840, WO99/15538 andDE10030638 describe multistage processes for preparing racemicmetallocene complexes via biphenoxide- or bisphenoxide-substitutedmetallocenes as intermediates. These approaches lead to metallocenessubstituted at zirconium with oxide or amide moieties. Theseintermediates have to be converted to the corresponding dichlorides inorder to use them as catalyst components, thus adding extra steps to thesynthesis.

U.S. Pat. No. 5,304,614 describes 2,4,7-substituted trialkyl-substitutedmetallocenes, which were obtained as mixtures between the racemic andthe meso forms.

It is an object of this invention to provide novel ansa-metallocenestructures for the selective preparation of the racemic complexes, whichare virtually free of the meso isomer. Not to be bound by any particulartheory, the inventors postulate that in order to achieve an intrinsicracemoselectivity, the hindrance of the formation of the meso form mightbe achieved by steric hindrance of the formation of the meso form.Attaching two large aromatic substituents to the indenyl-moiety in the4- and in the 7-position should hinder the formation of the meso-form ofthe complexes. FIG. 1 illustrates this concept.

Another object of the present invention is to address the shortcoming ofthe state of the art metallocene compounds to provide metallocenes thatafford high melting point, high molar mass homopolymers and high molarmass copolymers at high productivities when used as components ofsupported catalysts under industrially relevant polymerizationconditions at temperatures of from 50° C. to 100° C.

Another objective of the present invention is to provide a process forthe polymerization of olefins, particularly propylene, ethylene, andoptionally one or more higher 1-olefins.

Furthermore, it is an objective of the present invention to provideolefin polymers, particularly propylene homopolymers, random copolymersof propylene with ethylene and/or higher 1-olefins, impact copolymerscomprised of propylene, ethylene and/or optionally higher 1-olefins, andrandom impact copolymers comprised of propylene, ethylene and/oroptionally higher 1-olefins.

SUMMARY OF THE INVENTION

A metallocene compound having formula 1 below is provided herein,wherein the 4- and 7-positions (corresponding to the substituents R⁵ andR⁸, respectively) on the indenyl moiety possess large aromaticsubstituents. The metallocene compound is prepared in accordance with amethod which produces substantially pure racemic isomer. Advantageously,polymerisation catalysts comprising the metallocene of the inventionprovide superior olefin polymerisation results.

BRIEF DESCRIPTION OF THE DRAWINGS

Various embodiments are described below with reference to the drawingswherein:

FIG. 1 is a diagrammatic illustration of the steric effects of attachingtwo large aromatic substituents in the 4- and 7-positions of the indenylmoiety (corresponding to the substituents R⁵ and R⁸, respectively, informula 1); and

FIG. 2 is a diagrammatic illustration of individual steps of the processof the invention for producing transition-metal compounds of formula 1.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

Surprisingly it was found that bridged bis-indenyl ligands with aspecial substitution pattern lead selectively to racemicansa-metallocenes. Particularly, as shown in FIG. 1, when the 4- and7-positions on the indenyl moiety (corresponding to the substituents R⁵and R⁸, respectively) possess large aromatic constituents the affects ofsteric hinderance prevent the formation of the meso isomer of themetallocene. Instead, the product of the method of the present inventionis substantially pure racemic isomer as synthesized without any need forfurther separation processes. By “substantially pure” is meant at least90% racemic isomer, preferably at least 95% racemic isomer, and morepreferably at least 99% racemic isomer.

The first embodiment of the invention relates to a specificallysubstituted, bridged metallocene component of the general Formula 1below:

in which:

-   M¹ is a metal of the Groups 4-6 of the Periodic Table of the    Elements,-   R¹ and R² are identical or different and are each a hydrogen atom,    an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group    of from 1 to about 10 carbon atoms, an aryl group of from 6 to about    20 carbon atoms, an aryloxy group of from 6 to about 10 carbon    atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH    group, a halogen atom, or a NR₂ ³² group, where R³² is an alkyl    group of from 1 to about 10 carbon atoms or an aryl group of from 6    to about 14 carbon atoms and R¹ and R² may form one or more ring    system(s).-   R³ and R^(3′) are identical or different and are each a hydrogen    atom, a linear, cyclic or branched hydrocarbon group which may be    halogenated and/or may contain one or more hetero atoms like Si, B,    Al, O, S, N or P, for example an alkyl group of from 1 to about 20    carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon    atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an    alkylarylalkenyl group of from 9 to about 40 carbon atoms, an    arylalkyl group of 7 to 20 carbon atoms, an alkoxy group of from 1    to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon    atoms, a heteroaryl group of 3 to about 20 carbon atoms, an aryloxy    group of from 6 to about 10 carbon atoms, a silyloxy group of about    3 to 20 carbon atoms, an alkenyl group of from 2 to about 10 carbon    atoms, a halogen atom, or a NR₂ ³² group, where R³² is an alkyl    group of from 1 to about 10 carbon atoms or an aryl group of from 6    to about 14 carbon atoms,-   R⁴ and R^(4′) are identical or different and are each a hydrogen    atom, a linear, cyclic or branched hydrocarbon group which may be    halogenated and/or may contain one or more hetero atoms like Si, B,    Al, O, S, N or P, for example an alkyl group of from 1 to about 20    carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon    atoms, an alkylaryl group of from 7 to about 40 carbon atoms, or an    alkylarylalkenyl group of from 9 to about 40 carbon atoms, an    arylalkyl group of 7 to 20 carbon atoms, an alkoxy group of from 1    to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon    atoms, a heteroaryl group of 3 to about 20 carbon atoms, an aryloxy    group of from 6 to about 10 carbon atoms, a silyloxy group of about    3 to 20 carbon atoms, an alkenyl group of from 2 to about 10 carbon    atoms, a halogen atom, or a NR₂ ³² group, where R³² is an alkyl    group of from 1 to about 10 carbon atoms or an aryl group of from 6    to about 14 carbon atoms,-   R⁵, R^(5′), R⁸ and R^(8′) are identical or different and are each an    aryl group of from 6 to about 40 carbon atoms, an alkylaryl group of    from 7 to about 40 carbon atoms, or an alkenylaryl group of from 8    to about 40 carbon atoms or a substituted or unsubstituted silylaryl    group, or an (alkyl)(silyl)aryl group. The groups may contain one or    more hetero atoms like Si, B, Al, O, S, N or P, and/or may contain    halogen atoms like F, Cl or Br,-   R⁶, R^(6′), R⁷ and R^(7′) are identical or different and are each a    hydrogen atom, a linear, cyclic or branched hydrocarbon group which    may be halogenated and/or may contain one or more hetero atoms like    Si, B, Al, O, S, N or P, for example an alkyl group of from 1 to    about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20    carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms,    or an alkylarylalkenyl group of from 9 to about 40 carbon atoms, an    arylalkyl group of 7 to 20 carbon atoms, an alkoxy group of from 1    to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon    atoms, a heteroaryl group of 3 to about 20 carbon atoms, an aryloxy    group of from 6 to about 10 carbon atoms, a silyloxy group of about    3 to 20 carbon atoms, an alkenyl group of from 2 to about 10 carbon    atoms, a halogen atom, or a NR₂ ³² group, where R³² is an alkyl    group of from 1 to about 10 carbon atoms or an aryl group of from 6    to about 14 carbon atoms,-   R¹⁰ is a bridging group wherein R¹⁰ is selected from:

where

R⁴⁰ and R⁴¹, even when bearing the same index, can be identical ordifferent and are each a hydrogen atom, a C₁-C₄₀ group such as an alkylgroup having from 1 to about 30 carbon atoms, an aryl group of from 6 toabout 40 carbon atoms, a fluoroalkyl group of from 1 to about 10 carbonatoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryloxygroup of from 6 to about 10 carbon atoms, an alkenyl group of from 2 toabout 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbonatoms, an alkylaryl group of from 7 to about 40 carbon atoms, asubstituted or unsubstituted alkylsilyl, alkyl(aryl)silyl or arylsilylgroup or an arylalkenyl group of from 8 to about 40 carbon atoms. R⁴⁰and R⁴¹ together with the atoms connecting them can form one or morecyclic systems or R⁴⁰ and/or R⁴¹ can contain additional hetero atoms(i.e., non-carbon atoms) like Si, B, Al, O, S, N or P or halogen atomslike Cl or Br,

x is an integer from 1 to 18,

M¹² is silicon, germanium or tin, and

R¹⁰ may also link two units of the formula 1 to one another.

Preferred are compounds of the formula 1 in which

-   M¹ is a metal of the Group 4 of the Periodic Table of the Elements,-   R¹ and R² are identical or different and are each an alkyl group of    from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about    10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms    or a halogen atom, or R¹ and R² together may form one or more ring    system(s),-   R³ and R^(3′) are identical or different and are each a linear,    cyclic or branched hydrocarbon group which may be halogenated and/or    may contain one or more hetero atoms like Si, B, Al, O, S, N or P,    for example an alkyl group of from 1 to about 10 carbon atoms, an    alkylalkenyl group of from 3 to about 10 carbon atoms, an alkylaryl    group of from 7 to about 20 carbon atoms, or an alkylarylalkenyl    group of from 9 to about 20 carbon atoms, an arylalkyl group of 7 to    15 carbon atoms, an alkoxy group of from 1 to about 6 carbon atoms,    an aryl group of from 6 to about 10 carbon atoms, a heteroaryl group    of 3 to about 10 carbon atoms, an aryloxy group of from 6 to about    10 carbon atoms, a silyloxy group of about 3 to 10 carbon atoms, an    alkenyl group of from 2 to about 6 carbon atoms, a halogen atom, or    a NR₂ ³² group, where R³² is an alkyl group of from 1 to about 10    carbon atoms or an aryl group of from 6 to about 10 carbon atoms.-   R⁴ and R^(4′) are identical or different and are each a hydrogen    atom, a linear, cyclic or branched hydrocarbon group which may be    halogenated and/or may contain one or more hetero atoms like Si, B,    Al, O, S, N or P, for example an alkyl group of from 1 to about 20    carbon atoms,-   R⁵, R^(5′), R⁸ and R^(8′) are identical or different and are each an    aryl group of from 6 to about 40 carbon atoms, an alkylaryl group of    from 7 to about 40 carbon atoms. The groups may contain one or more    hetero atoms like B, Al, O, S, N or P, and/or may contain halogen    atoms like F, Cl or Br.-   R⁶, R^(6′), R⁷ and R^(7′) are identical or different and are each a    hydrogen atom, a linear, cyclic or branched hydrocarbon group which    may be halogenated and/or may contain one or more hetero atoms like    B, Al, O, S, N or P, for example an alkyl group of from 1 to about    20 carbon atoms.-   R¹⁰ is R⁴⁰R⁴¹Si═, R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where    R⁴⁰ and R⁴¹ are identical or different and are each a hydrogen atom,    a hydrocarbon group of from 1 to about 30 carbon atoms, in    particular an alkyl group of from 1 to about 10 carbon atoms, an    aryl group of from 6 to about 40 carbon atoms, an arylalkyl group of    from 7 to about 14 carbon atoms, an alkylaryl group of from 7 to    about 14 carbon atoms,

Particularly preferred are compounds of the formula 1 in which

-   M¹ is Zirconium,-   R¹ and R² are identical and are methyl, chlorine or phenolate,-   R³ and R^(3′) are identical and are a linear, cyclic or branched    alkyl group like methyl, ethyl, n-propyl, i-propyl, cyclopropyl,    n-butyl, t-butyl, t-butyl-methyl, i-butyl, s-butyl, n-pentyl,    n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl-methyl,    cyclopentyl, cyclopentyl-methyl, cyclohexyl, cyclohexyl-methyl,    (1-adamantyl)methyl, (2-adamantyl)methyl, or an arylalkyl group of 7    to 15 carbon atoms like benzyl, phenethyl or phenyl-propyl,-   R⁴ and R^(4′) are identical and are each a hydrogen atom,-   R⁵, R^(5′), R⁸ and R^(8′) are identical and are each an aryl group    of from 6 to about 20 carbon atoms, like phenyl, 1-naphthyl,    2-naphtyl, an alkylaryl group of from 7 to about 40 carbon atoms    which may contain one or more hetero atoms like B, Al, O, S, N or P,    and/or may contain halogen atoms like F, Cl or Br, like    4-methyl-phenyl, 4-ethyl-phenyl, 4-i-propyl-phenyl,    4-t-butyl-phenyl, 3,5-dimethylphenyl,    3,5-di-t-butyl-4-methoxy-phenyl, 2,3,4,5,6-pentafluorophenyl,-   R⁶, R^(6′), R⁷ and R^(7′) are identical and are each a hydrogen    atom.    The bridging unit R¹⁰ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹    are identical or different and are methyl, ethyl, propyl, butyl,    pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,    cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl, naphthyl, benzyl    or 3,3,3-trifluoropropyl.

Very particularly preferred are compounds of the formula 1 in which

-   M¹ is Zirconium,-   R¹ and R² are identical and are methyl or chlorine,-   R³ and R^(3′) are identical and are a linear, cyclic or branched    alkyl group like methyl, n-heptyl, n-octyl, n-nonyl, n-decyl,    cyclohexyl-methyl, t-butyl-methyl, (2-adamantyl)methyl,    (1-adamantyl)methyl, or an arylalkyl group of 7 to 15 carbon atoms    like benzyl, phenethyl or phenyl-propyl,-   R⁴ and R^(4′) are identical and are each a hydrogen atom,-   R⁵, R^(5′), R⁸ and R^(8′) are identical and are each an aryl group    of from 6 to about 20 carbon atoms, like phenyl, 1-naphthyl,    2-naphtyl, an alkylaryl group of from 7 to about 40 carbon atoms    which may contain one or more hetero atoms like B, Al, O, S, N or P,    and/or may contain halogen atoms like F, Cl or Br, like    4-methyl-phenyl, 4-ethyl-phenyl, 4-i-propyl-phenyl,    4-t-butyl-phenyl, 3,5-dimethylphenyl,    3,5-di-t-butyl-4-methoxy-phenyl, 2,3,4,5,6-pentafluorophenyl,-   R⁶, R^(6′), R⁷ and R^(7′) are identical and are each a hydrogen    atom.

The bridging unit R¹⁰ is R⁴⁰R⁴¹Si═ or R⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ areidentical or different and are methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl,cyclopentadienyl, cyclohexyl, phenyl, naphthyl, benzyl or3,3,3-trifluoropropyl.

Non-limiting examples for the metallocene compounds according to Formula1 are:

-   Dimethylsilanediylbis(2-methyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-ethyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-propyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-i-propyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-butyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-s-butyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-pentyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-hexyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-heptyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-methyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2,4,7-triphenyl-indenyl)zirconium dichloride;-   Dimethylsilanediylbis(2-benzyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenethyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylpropyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylbutyl-4,7-diphenyl-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-methyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-ethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-propyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-i-propyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-butyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-s-butyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-benzyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-methyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-ethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-propyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-i-propyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-butyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-s-butyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-benzyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-methyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-ethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-propyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-i-propyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-butyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-s-butyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-benzyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-methyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-ethyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-propyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-i-propyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-butyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-s-butyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-benzyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenethyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(1-naphthyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-methyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-ethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-propyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-i-propyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-butyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-s-butyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-benzyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride;-   Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride; and,-   Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(9-anthracenyl)-indenyl)zirconium    dichloride.

Another embodiment of this invention are the indenes of the formula 1aand the bis-indenyl-ligands of the formula 1b, as well as its doublebond-isomers:

in which R³, R^(3′), R⁴, R^(4′), R⁵, R^(5′), R⁶, R^(6′), R⁷, R^(7′), R⁸,R^(8′) and R¹⁰ have the meaning mentioned above with the proviso that R³and R^(3′) each contain at least one carbon atom.

The present invention also includes a process for the racemoselectiveproduction of the transition-metal compounds of formula 1 of theinvention comprising the following steps:

-   a) Deprotonation of the compound of formula 1a with a base,    preferably n-butyl lithium.-   b) If R¹⁰ has the meaning M¹²R⁴⁰R⁴¹, where M¹², R⁴⁰, and R⁴¹ have    the meanings specified above, then the further production proceeds    by the reaction of the deprotonated compounds from step (a) with    R⁴⁰R⁴¹M¹²X₂ to form the compound of formula 1b, where R⁴⁰, R⁴¹, and    M¹² have the meanings specified above, and X may be the same or    different and means a halogen atom, preferably chlorine, bromine, or    iodine, or another leaving group, preferably triflate, tosylate, or    mesylate.-   c) Double deprotonation of the compound of formula 1b with a base,    preferably n-butyl lithium.-   d) Reacting the product from step c) M¹Cl₄, in which M¹ stands for    zirconium, titanium, or hafnium, to form the compound of formula 1.

In step a), the compound of formula 1a, for example,2-methyl-4,7-bis-(4-t-butylphenyl)indene in an inert solvent, whichconsists of one or more aromatic or aliphatic hydrocarbons and/or one ormore polar, aprotic solvents, is deprotonated with a strong base, forexample, n-butyl lithium. The deprotonation is carried out attemperatures of −70° C. to 80° C., and preferably 0° C. to 80° C. Theresulting metal salt is then reacted directly, without furtherisolation, in step b) with a silicon compound or germanium compound thatcontains two leaving groups. Preferential production of the compound offormula 1b can be achieved by adjustment of the quantitativeproportions. In the following step c), the bis(indenyl)silanes offormula 1b are doubly deprotonated with a strong base, such as n-butyllithium, in an inert solvent, which consists of one or more aromatic oraliphatic hydrocarbons and/or one or more polar, aprotic solvents, andthe bislithium salt formed in this way is reacted, without isolation,directly with a source of Ti, Zr, or Hf to obtain the compound offormula 1. The deprotonation is carried out at temperatures of 70° C. to80° C., and preferably 0° C. to 80° C. Due to the nature of the ligandsystem of formula 1b, the metallocenes are isolated directly from thereaction mixture as pure racemic compounds.

In FIG. 2, the individual steps of the process of the invention forproducing transition-metal compounds of formula 1 are shown once againfor the example of a preferred embodiment.

In addition, the present invention relates to a catalyst systemcomprising at least one compound of formula 1 and at least onecocatalyst.

A suitable cocatalyst component which may be present according to thepresent invention in the catalyst system comprises at least one compoundof the type of an aluminoxane, a Lewis acid or an ionic compound whichreacts with a metallocene to convert the latter into a cationiccompound.

Aluminoxanes are oligomeric or polymeric aluminum oxy compounds, whichmay exist in the form of linear, cyclic, caged or polymeric structures.Although the exact structure(s) of aluminoxanes is still unknown, it iswell accepted that alkylaluminoxanes have the general formula 6.(R-AI-O)_(p)  (Formula 6).

Examples for cyclic, linear or cage structures of aluminoxanes aredepicted in the formulas 7, 8 and 9:

The radicals R in the formulas (6), (7), (8) and (9) can be identical ordifferent and are each a C₁-C₂₀ group such as an alkyl group of from 1to about 6 carbon atoms, an aryl group of from 6 to about 18 carbonatoms, benzyl or hydrogen and p is an integer from 2 to 50, preferablyfrom 10 to 35.

Preferably, the radicals R are identical and are methyl, isobutyl,n-butyl, phenyl or benzyl, particularly preferably methyl.

If the radicals R are different, they are preferably methyl andhydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen,isobutyl or n-butyl preferably being present in a proportion of from0.01 to 40% (number of radicals R).

The aluminoxane can be prepared in various ways by known methods. One ofthe methods comprises the reaction of an aluminum-hydrocarbon compoundand/or a hydridoaluminum-hydrocarbon compound with water, which may begaseous, solid, liquid or bound as water of crystallization, in an inertsolvent such as toluene. To prepare an aluminoxane having differentalkyl groups R, two different trialkylaluminums (AlR₃+AlR′₃)corresponding to the desired composition and reactivity are reacted withwater, cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0 302 424.

Regardless of the method of preparation, all aluminoxane solutions havein common a variable content of unreacted aluminum starting compoundwhich is present in free form or as an adduct.

Furthermore, instead of the aluminoxane compounds of the formulas 6, 7,8 or 9, it is also possible to use modified aluminoxanes in which thehydrocarbon radicals or hydrogen atoms have been partly replaced byalkoxy, aryloxy, siloxy or amide radicals.

The amounts of aluminoxane and metallocene used in the preparation ofthe supported catalyst system can be varied within a wide range.However, it has been found to be advantageous to use the metallocenecompound of formula 1 and the aluminoxane compounds in such amounts thatthe atomic ratio of aluminum from the aluminoxane compounds to thetransition metal from the metallocene compound is in the range from 10:1to 1000:1, preferably from 20:1 to 500:1 and in particular in the rangefrom 30:1 to 400:1. In the case of methylaluminoxane, preference isgiven to using 30 wt.-% strength toluene solutions, but the use of 10wt.-% strength solutions is also possible.

As Lewis acid, preference is given to using compounds of the formula 10M²X¹X²X³  (Formula 10)where

M² is an element of Group 13 of the Periodic Table of Elements, inparticular B, Al or Ga, preferably B or Al, and

X¹, X² and X³ are the same or different and each are a hydrogen atom, analkyl group of from 1 to about 20 carbon atoms, an aryl group of from 6to about 15 carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryleach having from 1 to 10 carbon atoms in the alkyl radical and from 6-20carbon atoms in the aryl radical or fluorine, chlorine, bromine oriodine. Preferred examples for X¹, X² and X³ are methyl, propyl,isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as arylor haloaryl like phenyl, tolyl, benzyl groups, p-fluorophenyl,3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl,3,4,5-trifluorophenyl and 3,5-di(trifluoromethyl)phenyl.

Preferred Lewis acids are trimethylaluminum, triethylaluminum,triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane,tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane,tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane,tris(penta-fluorophenyl)borane, tris(tolyl)borane,tris(3,5-dimethyl-phenyl)borane, tris(3,5-difluorophenyl)borane and/ortris(3,4,5-trifluorophenyl)borane.

Particular preference is given to tris(pentafluorophenyl)borane.

As ionic cocatalysts, preference is given to using compounds whichcontain a non-coordinating anion such astetrakis(pentafluorophenyl)borate, tetraphenylborate, SbF₆ ⁻, CF₃SO₃ ⁻or ClO₄ ⁻. Suitable counterions are either Lewis acid or Broenstedt acidcation.

As Broensted acids, particular preference is given to protonated amineor aniline derivatives such as methylammonium, anilinium,dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium,N,N-dimethylanilinium, trimethylammonium, triethylammonium,tri-n-butylammonium, methyldiphenylammonium, pyridinium,p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium,

Suitable Lewis-acid cations are cations of the formula 11[(Y^(a+))Q₁Q₂ . . . Q_(z)]^(d+)  (Formula 11)where Y is an element of Groups 1 to 16 of the Periodic Table of theElements, Q₁ to Q_(z) are singly negatively charged groups such asC₁-C₂₈-alkyl, C₆-C₁₅-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryleach having from 6 to 20 carbon atoms in the aryl radical and from 1 to28 carbon atoms in the alkyl radical, cycloalkyl groups of from 3 toabout 10 carbon atoms, which may in turn bear alkyl groups of from 1 toabout 10 carbon atoms as substitutents, halogen, alkoxy groups of from 1to 28 carbon atoms, aryloxy groups of from 6 to 15 carbon atoms, silylor mercaptyl groups.

a is an integer from 1-6,

z is an integer from 0 to 5 and

d corresponds to the difference a-z, but d is larger than or equal to 1

Particularly suitable cations are carbonium cations such astriphenylcarbenium, oxonium cations, sulfonium cations such astetrahydrothiophenium, phosphonium cations such as triethylphosphonium,triphenylphosphonium and diphenylphosphonium, and also cationictransition metal complexes such as the silver cation and the1,1′-dimethylferrocenium cation.

Preferred ionic compounds which can be used according to the presentinvention include:

-   triethylammoniumtetra(phenyl)borate,-   tributylammoniumtetra(phenyl)borate,-   trimethylammoniumtetra(tolyl)borate,-   tributylammoniumtetra(tolyl)borate,-   tributylammoniumtetra(pentafluorophenyl)borate,-   tributylammoniumtetra(pentafluorophenyl) aluminate,-   tripropylammoniumtetra(dimethylphenyl)borate,-   tributylammoniumtetra(trifluoromethylphenyl) borate,-   tributylammoniumtetra(4-fluorophenyl)borate,-   N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,-   N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate-   N,N-dimethylaniliniumtetra(phenyl)borate,-   N,N-diethylaniliniumtetra(phenyl)borate,-   N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,-   N,N-dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,-   di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,-   di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate,-   triphenylphosphoniumtetrakis(phenyl)borate,-   triethylphosphoniumtetrakis(phenyl)borate,-   diphenylphosphoniumtetrakis(phenyl)borate,-   tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,-   tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,-   triphenylcarbeniumtetrakis(pentafluorophenyl)borate,-   triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,-   triphenylcarbeniumtetrakis(phenyl)aluminate,-   ferroceniumtetrakis(pentafluorophenyl)borate and/or-   ferroceniumtetrakis(pentafluorophenyl)aluminate,

Preference is given totriphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate orN,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.

It is also possible to use mixtures of all of the above and belowmentioned cation-forming compounds. Preferred mixtures comprisealuminoxanes and an ionic compound, and/or a Lewis acid.

Other useful cocatalyst components are likewise borane or carboranecompounds such as

-   7,8-dicarbaundecaborane(13),-   undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane,-   dodecahydrido-1-phenyl-1,3-dicarbanonaborane,-   tri(butyl)ammoniumun decahydrido-8-ethyl-7,9-dicarbaundecaborate,-   4-carbanonaborane(14),-   bis(tri(butyl)ammonium)nonaborate,-   bis(tri(butyl)ammonium)undecaborate,-   bis(tri(butyl)ammonium)dodecaborate,-   bis(tri(butyl)ammonium)decachlorodecaborate,-   tri(butyl)ammonium-1-carbadecaborate,-   tri(butyl)ammonium-1-carbadodecaborate,-   tri(butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,-   tri(butyl)ammoniumbis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III),    tri(butyl)ammonium-   bis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III).

The amount of Lewis acids or ionic compounds having Lewis-acid orBroensted-acid cations is preferably from 0.1 to 20 equivalents,preferably from 1 to 10 equivalents, based on the metallocene compoundof the formula 1.

Combinations of at least one Lewis base with bimetallic compounds of thetype R_(i) ¹⁷M³(—O-M³R_(j) ¹⁸)_(v) or R_(i) ¹⁸M³(—O-M³R_(j) ¹⁷)_(v)(formula 12), as described in Patent Application WO 99/40,129, arelikewise important as cocatalyst systems.

In this regard, R¹⁷ and R¹⁸ are the same or different and represent ahydrogen atom, a halogen atom, a C₁-C₄₀ carbon-containing group,especially an alkyl group of from 1 to about 20 carbon atoms, haloalkylof from 1 to about 20 carbon atoms, alkoxy of from 1 to about 10 carbonatoms, aryl of from 6 to about 20 carbon atoms, haloaryl of from 6 toabout 20 carbon atoms, aryloxy of from 6 to about 20 carbon atoms,arylalkyl of from 7 to about 40 carbon atoms, haloarylalkyl of from 7 toabout 40 carbon atoms, alkylaryl of from 7 to about 40 carbon atoms, orhaloalkylaryl of from 7 to about 40 carbon atoms. R¹⁷ may also be an—OSiR⁵¹ ₃ group, in which the R⁵¹ groups are the same or different andhave the same meaning as R¹⁷, M³ is the same or different and representsan element of main group III of the periodic table of elements, i, j,and v each stands for a whole number 0, 1, or 2, and i+j+v is not equalto 0.

Preferred cocatalyst systems are the compounds of formulas (A) and (B)

where R¹⁷ and R¹⁸ have the same meaning as specified above.

Furthermore, compounds that are generally to be regarded as preferredare those formed by the reaction of at least one compound of formulas(C) and/or (D) and/or (E) with at least one compound of formula (F).

in which

-   R²⁷ may be a hydrogen atom or a boron-free C₁-C₄₀ carbon-containing    group, such as an alkyl of from 1 to about 20 carbon atoms, aryl of    from 6 to about 20 carbon atoms, arylalkyl of from 7 to about 40    carbon atoms, and alkylaryl of from 7 to about 40 carbon atoms, and    in which R¹⁷, R¹⁸ have the same meaning as specified above,-   D is an element of main Group VI of the periodic table of elements    or an NR⁶¹ group, where R⁶¹ is a hydrogen atom or a C₁-C₂₀    hydrocarbon group, such as alkyl of from 1 to about 20 carbon atoms    or aryl of from 6 to about 20 carbon atoms,-   f is a whole number from 0 to 3,-   g is a whole number from 0 to 3 where f+g corresponds to the valency    of Boron, and-   h is a whole number from 1 to 10.

The bimetallic compounds of formula 12 are possibly combined with anorganometallic compound of formula 13, i.e., [M⁴R¹⁹ _(q)]_(k), in whichM⁴ is an element of main Group I, II, or III of the periodic table ofthe elements, R¹⁹ is the same or different and represents a hydrogenatom, a halogen atom, a C₁-C₄₀ carbon-containing group, an alkyl groupof from 1 to about 20 carbon atoms, an aryl group of from about 6 toabout 40 carbon atoms, arylalkyl of from 7 to about 40 carbon atoms, andalkylaryl of from 7 to about 40 carbon atoms, q is a whole number from 1to 3, and k is a whole number from 1 to 4.

The organometallic compounds of formula 13 are preferably neutral Lewisacids, in which M⁴ stands for lithium, magnesium, and/or aluminum,especially aluminum. Examples of preferred organometallic compounds offormula 13 are trimethylaluminum, triethylaluminum,triisopropylaluminum, trihexylaluminum, trioctylaluminum,tri-n-butylaluminum, tri-n-propylaluminum, triisoprene aluminum,dimethyl aluminum monochloride, aluminum monochloride, diisobutylaluminum monochloride, methyl aluminum sesquichloride, ethyl aluminumsesquichloride, dimethyl aluminum hydride, aluminum hydride, diisopropylaluminum hydride, dimethyl aluminum(trimethylsiloxide), dimethylaluminum(triethylsiloxide), phenylalan, pentafluorophenylalan, ando-tolylalan.

The catalyst system of the invention contains an organoboroaluminumcompound, which contains units of formula 12, as the cocatalyticallyactive chemical compound. Compounds of formula 12 in which M³ stands forboron or aluminum are preferred. The compounds that contain units offormula 12 may be present as monomers or as linear, cyclic, or cage-likeoligomers. Two or more chemical compounds that contain units of formula12 may also form dimers, trimers, or higher combinations amongthemselves by Lewis acid-base interactions.

Preferred cocatalytically active bimetallic compounds correspond toformulas 14 and 15,

in which R¹⁰⁰ and R²⁰⁰ are the same or different and have the samemeaning as the substituents R¹⁷ or R¹⁸ in formula 12.

Examples of the cocatalytically active compounds of formulas 14 and 15are

The compounds named in EP-A-924,223, DE 196 22 207.9, EP-A-601,830,EP-A-824,112, EP-A-824,113, WO 99/06,414, EP-A-811,627, WO 97/11,775, DE196 06 167.9 and DE 198 04 970 can be used as additional cocatalysts,which may be present in unsupported or supported form.

The amount of cocatalysts of formula 12 and/or 14 and/or 15 used in thecatalyst of the present invention can vary from 0.1 to 500 equivalents,preferably from 1 to 300 equivalents, most preferably from 5 to 150equivalents, based on the used amount of metallocene compound of theformula 1.

The catalyst system of the present invention can further comprise, asadditional component, a metal compound of the formula 16,M⁵(R²²)_(r)(R²³)_(s)(R²⁴)_(t)  (Formula 16)wherein

-   -   M⁵ is an alkali, an alkali earth metal or a metal of Group 13 of        the Periodic Table of the Elements,    -   R²² is a hydrogen atom, alkyl of from 1 to about 10 carbon        atoms, aryl of from 6 to about 15 carbon atoms, or alkylaryl or        arylalkyl each having from 1 to 10 carbon atoms in the alkyl        part and from 6 to 20 carbon atoms in the aryl part,    -   R²³ and R²⁴ are each a hydrogen atom, a halogen atom, alkyl of        from 1 to about 10 carbon atoms, C₆-C₁₅-aryl of from about 6 to        about 15 carbon atoms, or alkylaryl, arylalkyl or alkoxy each        having from 1 to 10 carbon atoms in the alkyl part and from 6 to        20 carbon atoms in the aryl radical,    -   r is an integer from 1 to 3 and s and t are integers from 0 to        2, where the sum r+s+t corresponds to the valency of M⁵,        where this component is not identical with the above mentioned        cocatalyst compounds. It is also possible to use mixtures of        various metal compounds of the formula 16.

Among the metal compounds of the formula 16 preference is given to thosein which M⁵ is lithium, magnesium or aluminum and R²³ and R²⁴ are eachalkyl of from 1 to about 10 carbon atoms. Particularly preferred metalcompounds of the formula 16 are n-butyllithium,n-butyl-n-octyl-magnesium, n-butyl-n-heptylmagnesium,tri-n-hexylaluminum, triisobutylaluminum, triethylaluminum,trimethylaluminum or mixtures thereof.

If a metal compound of the formula 16 is used, it is preferably presentin the catalyst system in such an amount that the molar ratio of M⁵ tothe transition metal from the metallocene compound of formula 1 is from800:1 to 1:1, in particular from 200:1 to 2:1.

The support component of the catalyst system of the present inventioncan be any organic or inorganic inert solid or a mixture of such solids,in particulate porous solids such as hydrotalcites, talc, inorganicoxides and finely divided polymer powders.

Suitable inorganic oxides, which are preferably employed include fromthe Periodic Table of Elements Groups 1, 2, 3, 4, 5, 12, 13 and 14 metaloxides such as silicon dioxide, aluminum oxide, aluminosilicates,zeolites, MgO, ZrO₂, TiO₂ or B₂O₃, CaO, ZnO, ThO₂, Na₂O, K₂O, LiO₂ ormixed oxides like Al/Si oxides, Mg/Al oxides or Al/Mg/Si oxides. Othersuitable inorganic support materials are Na₂CO₃, K₂CO₃, CaCO₃, MgCl₂,Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂ and Al(NO₃)₃.

Suitable polymer powders are homopolymers, copolymers, crosslinkedpolymers or polymer blends. Examples of such polymers are polyethylene,polypropylene, polybutene, polystyrene, divinylbenzene-crosslinkedpolystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrenecopolymer, polyamide, polymethacrylate, polycarbonate, polyester,polyacetal or polyvinyl alcohol.

The preferred support materials have a specific surface area in therange from 10 to 1000 m²/g, a pore volume in the range from 0.1 to 5cm³/g and a mean particle size of from 1 to 500 μm. Preference is givento supports having a specific surface area in the range from 50 to 500m²/g, a pore volume in the range from 0.5 to 3.5 cm³/g and a meanparticle size in the range from 5 to 250 μm. Particular preference isgiven to supports having a specific surface area in the range from 200to 400 m²/g, a pore volume in the range from 0.8 to 3.0 cm³/g and a meanparticle size of from 10 to 100 μm.

The support materials can be thermally and/or chemically be pretreatedin order to adjust certain properties of the carrier such as the waterand/or the hydroxyl group content.

If the support material has a low moisture content or residual solventcontent, dehydration or drying before use can be omitted. If this is notthe case, as when using silica gel as support material, dehydration ordrying is advisable. Thermal dehydration or drying of the supportmaterial can be carried out under reduced pressure with or withoutsimultaneous inert gas blanketing (nitrogen). The drying temperature isin the range from 80° C. to 1000° C., preferably from 150° C. to 800° C.and most preferred from 150° C. to 400° C. The duration of the dryingprocess can be from 1 to 24 hours. But shorter or longer drying periodsare also possible.

In a preferred embodiment of the present invention, support materialswith a weight loss on dryness (LOD) of 0.5 wt. % or less, and even morepreferred with a LOD of 0.3 wt % or less are used. Higher amounts ofphysically adsorbed water up to 1 wt % are possible, but result inreduced catalyst activities. The loss on ignition (LOI) of the supportmaterial is preferably 1 wt % or greater or even more preferred between1.5 and 3.5 wt %. The weight loss on dryness (LOD) is thereby defined asthe weight loss between room temperature and 300° C. and the weight losson ignition (LOI) as the weight loss between 300° C. and 1000° C.

In addition or alternatively, dehydration or drying of the supportmaterial can also be carried out by chemical means, by reacting theadsorbed water and/or the surface hydroxyl groups with suitablepassivating agents. Reaction with the passivating reagent can convertthe hydroxyl groups completely or partially into a form, which does notshow any adverse interaction with the catalytically active centers.Suitable passivating agents are silicon halides, silanes or amines, eg.silicon tetrachloride, chlorotrimethylsilane, dichlorodialkylsilanes,dimethylaminotrichlorosilane, N,N-dimethylanilin orN,N-dimethylbenzylamine or organometallic compounds of aluminum, boronand magnesium, eg. aluminoxanes, trimethylaluminum, triethylaluminum,triisobutylaluminum, diisobutylaluminum hydride, triethylborane ordibutylmagnesium.

As outlined above, organic support materials such as finely dividedpolymer powders, can also be used and should, before use, likewise befreed from any adhering moisture, solvent residues or other impuritiesby means of appropriate purification and drying operations.

Preference is given to using silica gels having the defined parametersas support materials. Spray dried silica grades, which inherentlyexhibit meso and macro pores, cavities and channels are preferred overgranular silica grades.

The supported catalyst system according to this invention can be made invarious ways.

In one embodiment of the present invention, at least one of theabove-described metallocene components of formula 1 is brought intocontact in a suitable solvent with at least one cocatalyst component,preferably giving a soluble reaction product, an adduct or a mixture.The obtained composition is mixed with the dehydrated or passivatedsupport material, the solvent is removed and the resulting supportedmetallocene catalyst system is dried to ensure that the solvent iscompletely or mostly removed from the pores of the support material. Thesupported catalyst is obtained as a free-flowing powder.

As an example, the process for preparing a free-flowing and, if desired,prepolymerized supported catalyst system comprises the following steps:

a) preparing a metallocene/cocatalyst mixture in a suitable solvent orsuspension medium, where the metallocene component has one of theabove-described structures,

b) applying the metallocene/cocatalyst mixture to a porous, preferablyinorganic, if necessary thermally or chemically pretreated support,

c) removing the major part of solvent from the resulting mixture,

d) isolating the supported catalyst system and

e) if desired, prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In another embodiment of this invention the metallocene/cocatalystcomposition is mixed with the dehydrated or passivated support material,the supported catalyst is recovered and optionally washed with anaromatic hydrocarbon and/or paraffinic hydrocarbon solvent. The isolatedcatalyst is then dispersed in a non-reactive suspension media such as aparaffinic hydrocarbon solvent, a mineral oil or a wax or mixturesthereof.

In a further embodiment of this invention the catalyst can be preparedaccording to the procedure disclosed in WO 06/60544, WO 00/05277 and WO98/01481.

As an example, in WO 06/60544, a free flowing and, if desired,prepolymerized supported catalyst system is prepared comprising thefollowing steps:

a) contacting at least one support material with a first portion of atleast one co-catalyst in a suitable solvent

b) impregnating the co-catalyst loaded support with a suspension orsolution, which comprises at least one metallocene and a second portionof at least one co-catalyst in a suitable solvent

c) isolating the supported catalyst system and

f) if desired, prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

Thus, as an example, the process according to WO 06/60544 for preparinga free-flowing and, if desired, prepolymerized supported catalyst systemcomprises the following steps:

a) Contacting a support material with a first composition which includesat least one aluminoxane in a first solvent at a temperature of about 10to 30° C. followed by keeping the mixture at about 20° C. for 0 to 12hours, subsequently heating the resulting mixture to a temperature of 30to 200° C. and keeping the mixture at 30 to 200° C. for 30 minutes to 20hours, optionally followed by removing all or part of the first solventand/or optionally followed by one or more washing step(s) using asuitable solvent,

b) Suspending and/or dissolving, respectively, at least one metalloceneof formula 1 and a second portion of an aluminoxane or of a mixture ofaluminoxanes or of an ionic compound and/or a Lewis acid in a secondsolvent or suspension medium at a temperature of 0 to 100° C.,optionally followed by a preactivation time of 1 minute to 200 hours ata temperature of 10 to 100°,

c) Applying the mixture prepared in b) to the aluminoxane loaded supportmaterial produced in a), at a temperature of 10 to 100° C. and a contacttime of 1 minute to 24 hours,

d) Removing the major part of the solvent from the resulting mixture andoptionally washing the resulting supported catalyst with a suitablesolvent,

e) Isolating the supported catalyst system and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

More specifically, as an example, the process according to WO 06/60544for preparing a free-flowing and, if desired, prepolymerized supportedcatalyst system comprises the following steps:

a) Contacting a support material with a first composition which includesat least 5 mmol of an aluminoxane or of a mixture of aluminoxanes per gsupport material in a first solvent at a temperature of about 20° C.followed by keeping the mixture at about 20° C. for 0.15 to 2 hours,subsequently heating the resulting mixture to a temperature of 50 to160° C. and keeping the mixture at 50 to 160° C. for 1 to 6 hours,optionally followed by removing all or part of the first solvent and/oroptionally followed by one or more washing step(s) using a suitablesolvent,

b) Suspending and/or dissolving, respectively, at least 0.5 mmole of asecond portion of an aluminoxane or of a mixture of aluminoxanes per gsupport material and at least 0.1 mol % of the employed second portionof an aluminoxane or of a mixture of aluminoxanes per g support materialof at least one metallocene of formula 1 in a second solvent orsuspension medium at a temperature of 20 to 50° C., optionally followedby a preactivation time of 1 minute to 200 hours at a temperature of 20to 30°,

c) Applying the mixture prepared in b) to the aluminoxane loaded supportmaterial produced in a), at a temperature of 10 to 100° C. and a contacttime of 1 minute to 24 hours,

d) Removing the major part of the solvent from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In a preferred embodiment, as an example, the process according to WO06/60544 for preparing a free-flowing and, if desired, prepolymerizedsupported catalyst system comprises the following steps:

a) Contacting an optionally thermally pretreated silica support materialwith at least 10 mmol of an aluminoxane per g support material intoluene at a temperature of about 20° C. followed by subsequentlyheating the resulting mixture to a temperature of 50 to 110° C. andkeeping the mixture at 50 to 110° C. for 1 to 6 hours, optionallyfollowed by removing all or part of the toluene, and/or optionallyfollowed by one or more washing step(s) using a suitable solvent,

b) Suspending and/or dissolving, respectively, at least 0.5 mmole of asecond portion of an aluminoxane per g support material and at least 0.1mol % of the employed second portion of an aluminoxane or of a mixtureof aluminoxanes per g support material of at least one metallocene offormula 1 in toluene at a temperature of 20 to 50° C., optionallyfollowed by a preactivation time of 1 minute to 200 hours at atemperature of 20 to 30°,

c) Applying the mixture prepared in b) to the aluminoxane loaded supportmaterial produced in a), at a temperature of 10 to 100° C. and a contacttime of 1 minute to 24 hours,

d) Removing the major part of the toluene from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In a more preferred embodiment, as an example, the process according toWO 06/60544 for preparing a free-flowing and, if desired, prepolymerizedsupported catalyst system comprises the following steps:

a) Contacting an optionally thermally pretreated silica support materialwith a weight loss on dryness (LOD) of 0.5 wt. % or less and a weightloss on ignition (LOI) of 1.0 wt. % or greater with a first compositionwhich includes at least 10 mmol of methylaluminoxane per g supportmaterial in toluene at a temperature of about 20° C. followed bysubsequently heating the resulting mixture to a temperature of 110° C.and keeping the mixture at 110° C. for 1 to 6 hours, optionally followedby removing all or part of the toluene, and/or optionally followed byone or more washing step(s) using a suitable solvent,

b) Suspending and/or dissolving, respectively, at least 1 mmole of asecond portion of methylaluminoxane per g support material and at least0.1 mol % of the employed second portion of methylaluminoxane per gsupport material of at least one metallocene of formula 1 in toluene ata temperature of 20 to 50° C., optionally followed by a preactivationtime of 1 minute to 200 hours at a temperature of 20 to 30°,

c) Applying the mixture prepared in b) to the methylaluminoxane loadedsupport material produced in a), by passing the impregnation suspensionor solution b) through the methylaluminoxane loaded support material ina direct flow or by using an incipient wetness impregnation technique,where the volume of the impregnation suspension or solution or the totalliquid volume used in the impregnation step, respectively, does notexceed 250% of the total pore volume of the support material, at atemperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,

d) Removing the major part of the toluene from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

In a particular preferred embodiment, as an example, the processaccording to WO 06/60544 for preparing a free-flowing and, if desired,prepolymerized supported catalyst system comprises the following steps:

a) Contacting an optionally thermally pretreated silica support materialwith a weight loss on dryness (LOD) of 0.3 wt. % or less and a weightloss on ignition (LOT) between 1.5 and 3.5 wt. %, with at least 10 mmolof methylaluminoxane per g support material in toluene at a temperatureof about 20° C. followed by subsequently heating the resulting mixtureto a temperature of 110° C. and keeping the mixture at 110° C. for 1 to6 hours, optionally followed by removing all or part of the toluene,and/or optionally followed by one or more washing step(s) using asuitable solvent,

b) Suspending and/or dissolving, respectively, at least 1 mmole of asecond portion of methylaluminoxane per g support material and at least0.1 mol % of the employed second portion of methylaluminoxane per gsupport material of at least one metallocene of formula 1 in toluene ata temperature of 20 to 50° C., optionally followed by a preactivationtime of 1 minute to 200 hours at a temperature of 20 to 30°,

c) Applying the mixture prepared in b) to the methylaluminoxane loadedsupport material produced in a), by passing the impregnation suspensionor solution b) through the aluminoxane loaded support material a) in adirect flow or by using an incipient wetness impregnation technique,where the volume of the impregnation suspension or solution or the totalliquid volume used in the impregnation step, respectively, does notexceed 250% of the total pore volume of the support material, at atemperature of 10 to 100° C. and a contact time of 1 minute to 24 hours,

d) Removing the major part of the toluene from the resulting mixture and

e) Optionally washing the resulting supported catalyst with a suitablesolvent, and/or drying the resulting supported catalyst at temperaturesof 30 to 60° C., and

f) Optionally prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

According to the present invention, for preparing a free-flowing and, ifdesired, prepolymerized supported catalyst system, in step b) of thecatalyst preparations as mentioned above, instead of an aluminoxane or amixture of aluminoxanes, at least one alkyl compound of elements of mainGroups I to III of the Periodic Table, for example a magnesium alkyl, alithium alkyl or an aluminum alkyl like trimethylaluminum,triethylaluminum, triisobutyllaluminum, triisopropylaluminum,trihexylaluminum, trioctylaluminum, tri-n-butylaluminum,tri-n-propylaluminum, triisoprene aluminum, dimethyl aluminummonochloride, aluminum monochloride, diisobutyl aluminum monochloride,methyl aluminum sesquichloride, ethyl aluminum sesquichloride, dimethylaluminum hydride, aluminum hydride, diisopropyl aluminum hydride,dimethyl aluminum(trimethylsiloxide), dimethylaluminum(triethylsiloxide), phenylalan, pentafluorophenylalan, ando-tolylalan, can be used. Preferred aluminum alkyls aretrimethylaluminum, triethylaluminum, triisobutyllaluminum.

In an even further embodiment of the present invention a free flowingand, if desired, prepolymerized supported catalyst system is preparedcomprising the following steps:

a) preparing a trialkylaluminium/borinic acid mixture in a suitablesolvent or suspension medium

b) applying the trialkylaluminium/borinic acid mixture to a porous,preferably inorganic, if necessary thermally or chemically pretreatedsupport, which was prior treated with a base likeN,N-diethylbenzylamine, N,N-dimethylbenzylamine, N-benzyldimethylamine,N-benzyldiethylamine, N-benzylbutylamine, N-benzyl tertbutylamine,N-benzylisopropylamine, N-benzylmethylamine, N-benzylethylamine,N-benzyl-1-phenylethylamine, N-benzyl-2-phenylethylamine,N,N-dimethylbenzylamine, N,N-diethylbenzylamine,N-methyl-N-ethylbenzylamine, N-methyldibenzylamine andN-ethyldi(benzyl)amine,

c) removing the major part of solvent from the resulting mixture toobtain a supported cocatalyst,

d) preparing a metallocene/supported cocatalyst mixture in a suitablesolvent or suspension medium, where the metallocene of formula 1 isoptionally treated with additional trialkylaluminum,

e) isolating the supported catalyst system and

f) if desired, prepolymerizing the resulting supported catalyst systemwith one or more olefinic monomer(s), to obtain a prepolymerizedsupported catalyst system.

Preferred solvents for the preparation of the metallocene/cocatalystmixture are hydrocarbons and hydrocarbon mixtures, which are liquid atthe selected reaction temperature and in which the individual componentspreferably dissolve. The solubility of the individual components is,however, not a prerequisite as long as it is ensured that the reactionproduct of metallocene and cocatalyst components is soluble in thesolvent selected. Suitable solvents are alkanes such as pentane,isopentane, hexane, isohexane, heptane, octane and nonane, cycloalkanessuch as cyclopentane and cyclohexane and aromatics such as benzene,toluene, ethylbenzene and diethylbenzene. Very particular preference isgiven to toluene, heptane and ethylbenzene.

For a preactivation, the metallocene in the form of a solid is dissolvedin a solution of the cocatalyst in a suitable solvent. It is alsopossible to dissolve the metallocene separately in a suitable solventand subsequently to combine this solution with the cocatalyst solution.Preference is given to using toluene. The preactivation time is from 1minute to 200 hours. The preactivation can take place at roomtemperature of 25° C. In individual cases, the use of highertemperatures can reduce the required preactivation time and give anadditional increase in activity. Elevated temperatures in this caserefer to a range from 25° C. to 100° C.

The preactivated solution or the metallocene/cocatalyst mixture issubsequently combined with an inert support material, usually silicagel, which is in the form of a dry powder or as a suspension in one ofthe above mentioned solvents. The support material is preferably used aspowder. The preactivated metallocene/cocatalyst solution or themetallocene/cocatalyst mixture can be either added to the initiallycharged support material, or else the support material can be introducedinto the initially charged solution.

The volume of the preactivated solution or the metallocene/cocatalystmixture can exceed 100% of the total pore volume of the support materialused or else be up to 100% of the total pore volume.

The temperature at which the preactivated solution or themetallocene/cocatalyst mixture is brought into contact with the supportmaterial can vary within the range from 0° C. to 100° C. However, loweror higher temperatures are also possible.

While the solvent is completely or mostly removed from the supportedcatalyst system, the mixture can be stirred and, if desired, alsoheated. Preferably, both the visible portion of the solvent and theportion in the pores of the support material are removed. The removal ofthe solvent can be carried out in a conventional way using reducedpressure and/or purging with inert gas. During the drying process, themixture can be heated until the free solvent has been removed, whichusually takes from 1 to 3 hours at a preferred temperature of from 30°C. to 60° C. The free solvent is the visible portion of the solvent inthe mixture. For the purposes of the present invention, residual solventis the portion present in the pores.

As an alternative to the complete removal of the solvent, the supportedcatalyst system can also be dried until only a certain residual solventcontent is left, with the free solvent having been completely removed.Subsequently, the supported catalyst system can be washed with alow-boiling point hydrocarbon such as pentane or hexane and dried again.

The supported catalyst system prepared according to the presentinvention can be used either directly for the polymerization of olefinsor be prepolymerized with one or more olefinic monomers, with or withoutthe use of hydrogen as molar mass regulating agent, prior to use in apolymerization process. The procedure for the prepolymerization ofsupported catalyst systems is described in WO 94/28034.

It is possible to add, during or after the preparation of the supportedcatalyst system, a small amount of an olefin, preferably an alpha-olefinsuch as styrene or phenyldimethylvinylsilane as activity-increasingcomponent or an antistatic, as described in U.S. Ser. No. 08/365,280.The molar ratio of additive to metallocene component of formula 1 ispreferably from 1:1000 to 1000:1, very particularly preferably from 1:20to 20:1.

The present invention also provides a process for preparing a polyolefinby polymerization of one or more olefins in the presence of the catalystsystem of the present invention comprising at least one transition metalcomponent of the formula 1. For the purposes of the present invention,the term polymerization refers to both homopolymerization andcopolymerization and the term copolymerization includesterpolymerisation or copolymerisation of more than three differentmonomers.

Preference is given to polymerizing olefins of the formulaR^(m)—CH═CH—R^(n), where R^(m) and R^(n) are identical or different andare each a hydrogen atom or a radical having from 1 to 20 carbon atoms,in particular from 1 to 10 carbon atoms, and R^(m) and R^(n) togetherwith the atoms connecting them can form one or more rings.

Suitable olefins are 1-olefins, eg. ethylene, propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienessuch as 1,3-butadiene, 1,4-hexadiene, vinylnorbornene, norbornadiene,ethylnorbornadiene and cyclic olefins such as norbornene,tetracyclododecene or methylnorbornene. In the process of the presentinvention, preference is given to homopolymerizing propylene or ethyleneor copolymerizing propylene with ethylene and/or one or more 1-olefinshaving from 4 to 20 carbon atoms, eg. 1-butene or hexene, and/or one ormore dienes having from 4 to 20 carbon atoms, eg. 1,4-butadiene,norbornadiene, ethylidenenorbornene or ethylnorbornadiene. Very suitablecopolymers are ethylene-propylene copolymers, propylene-1-pentenecopolymers and ethylene-propylene-1-butene, ethylene-propylene-1-penteneor ethylene-propylene-1,4-hexadiene terpolymers.

The polymerization is carried out at from −60° C. to 300° C., preferablyfrom 50° C. to 200° C., very particularly preferably from 50° C. to 95°C. The pressure is from 0.5 to 2000 bar, preferably from 5 to 100 bar.

The polymerization can be carried out in solution, in bulk, insuspension or in the gas phase, continuously or batchwise, in one ormore stages. As an example, impact copolymers are preferably produced inmore than one stage. The homopolymer or random copolymer content of sucha polymer can be produced in (a) first stage(s) and the copolymer rubbercontent can be produced in (a) consecutive stage(s).

The supported catalyst system prepared according to the presentinvention can be used as sole catalyst component for the polymerizationof olefins or preferably in combination with at least one alkyl compoundof elements of main Groups I to III of the Periodic Table, for examplean aluminum alkyl, magnesium alkyl or lithium alkyl or an aluminoxane.The alkyl compound is added to the monomer or suspension medium andserves to free the monomer of substances, which can impair the catalyticactivity. The amount of alkyl compound added depends on the quality ofthe monomers used.

To prepare olefin polymers having a broad or bimodal molecular weightdistribution or a broad or bimodal melting range, it is recommended touse a catalyst system comprising two or more different metallocenesand/or two or more different cocatalysts. Alternatively two or moredifferent catalyst systems of the present invention can be used as amixture.

As molar mass regulator and/or to increase the activity, hydrogen isadded if required.

The catalyst system may be supplied to the polymerization system as asolid or in the form of a paste or suspension in a hydrocarbon or may betreated with inert components, such as paraffins, oils, or waxes, toachieve better metering. If the catalyst system is to be metered intothe reactor together with the monomer to be polymerized or the monomermixture to be polymerized, the mixing unit and the metering line arepreferably cooled.

Furthermore, an additive such as an antistatic or an alcohol can be usedin the process of the present invention, for example to improve theparticle morphology of the olefin polymer. In general it is possible touse all antistatics which are suitable in olefin polymerizationprocesses. It is preferred to dose the antistatic directly into thepolymerization system, either together with or separately from thecatalyst system used.

The polymers prepared using the catalyst systems of the presentinvention display an uniform particle morphology and contain no fines.No agglomerates or deposits are obtained in the polymerization using thecatalyst system of the present invention.

The catalyst systems of the present invention give polymers such aspolypropylene having high molecular weight and cover a broad range ofstereospecificity and regiospecificity.

The copolymers which can be prepared using the catalyst system based onmetallocenes of formula 1 of the present invention have a significantlyhigher molar mass compared to the prior art. At the same time, suchcopolymers can be prepared using the catalyst system of the presentinvention at a high productivity and at industrially relevant processparameters without deposit formation.

The polymers prepared by the process of the present invention aresuitable, in particular, for producing products such as fibers,filaments, injection-molded parts, films, sheets, caps, closures,bottles or large hollow bodies such as pipes with excellent properties.

EXAMPLES

The Examples below illustrate the invention. The comparative examplesare presented for comparison purposes only and do not illustrate theinvention.

General Procedures

The preparation and handling of the organometallic compounds werecarried out under argon using Schlenk techniques or in a glove box. Allsolvents were purged with argon and dried over molecular sieves beforeuse.

The metallocenes produced were characterized by ¹H-NMR spectroscopyusing a Bruker DMX 500 spectrometer, operating at 500 MHz using CDCl₃ asthe solvent.

The polymers produced were characterized by ¹H-NMR, ¹³C-NMR, DSC, GPC,TREF/ATREF, Melt Flow Rate and IR spectroscopy.

1. Gel Permeation Chromatography (GPC), Determination of Mw and Mw/Mn

A Waters Alliance/GPCV2000 equipped with a refractometer, a triplecapillary on-line viscometer (Waters Corporation, 34 Maple Street,Milford, Mass., 01757 USA) and a light scattering detector PD 2040(Precision Detectors Inc., 34 Williams Way, Bellingham, Mass., USA) wasused for the determination of the molar mass data of the samples. 0.05wt % solutions of the samples in 1,2,4-trichlorobenzene were analyzed ata temperature of 145° C. using a Mixed B light scattering quality column(Polymer Labs 1110-6100LS) and a Mixed B guard column (Polymer Labs1110-1120). Weight average molar mass (Mw) and the ratio of weightaverage molar mass to number average molar mass (Mw/Mn) were calculatedusing the Cumulative Matching % Broad Standard procedure that isavailable in the Waters Millenium 3.2 GPC software module.

2. NMR Spectroscopy

Samples were prepared by weighing 0.32 g of polymer into 2.5 ml of a1,2,4-trichlorobenzene/deuterobenzene-d6 (4:1 volume) mixture. Sampleswere heated to 125° C. and mixed until a homogeneous solution was formed(typically 1-4 hours). Spectra were obtained at 120° C. on a VarianInova 500 instrument (Varian Inc., 3120 Hansen Way, Palo Alto, Calif.,94304, USA) operating at a ¹³C-spectrometer frequency of 125.7 MHz andusing a 10 mm probe. Spectra were obtained using 5000 scans employing aπ/2 pulse of 10.0 μs, a recycle delay of 10.0 s and an acquisition timeof 2.5 s. Waltz-16 decoupling remained on throughout the pulse sequenceto gain the signal to noise enhancement due to the effects of nOe.Spectra were processed with 1 Hz of line broadening. The mmmm peak inthe methyl region of the spectrum was used as an internal chemical shiftreference and was set to 21.85 ppm.

3. Differential Scanning Calorimetry (DSC), Determination of the PolymerMelting Point Tm

DSC measurements were carried out using a Mettler Toledo DSC 822e(Mettler-Toledo Inc., 1900 Polaris. Parkway, Columbus, Ohio, 43240,USA). 4 mg of sample were weighed into a standard aluminum pan andsubjected to the following temperature schedule:

The samples were heated from room temperature to 220° C. at a heatingrate of 20° C./min, maintained at this temperature for 5 min, thencooled down to −55° C. at a cooling rate of 20° C./min, maintained atthe same temperature for 5 min, then heated to 220° C. at a heating rateof 20° C./min. The melting point was determined from the second heatingrun as the temperature where the main peak was observed in the curve.

4. Analytical TREF (ATREF)

The TREF experiment is carried out on a TREF system built from amodified Waters 2000CV instrument (Waters Corporation, 34 Maple Street,Milford, Mass., 01757 USA). The 2000CV instrument is maintained at 140°C. in o-dichlorobenzene (ODCB) solvent at 1 ml/min flowrate. To detectthe polyolefin fractions eluting from the TREF column, the system uses aheated infrared IR4 detector (PolymerChar Company, Valencia TechnologyPark, P.O. Box 176, Valencia, Va., E-46980, PATERNA, Spain). For coolingand heating of the TREF column, the system uses atemperature-programmable HAAKE Phoenix II oil bath (Thermo ElectronCorporation, 401 Millcreek Road, Marietta, Ohio 45750, USA). The TREFseparation column is a stainless steel column of 100 mm long and 0.75 mmdiameter packed with 20-micrometer cross-linked polystyrene beads. ThisTREF column is maintained at the 140° C. temperature in the oil bathbefore the sample analyses. Polymer samples are dissolved in ODCBsolvent at 140° C. at a concentration of 2 mg/ml. One ml of the testsample of the resultant ODCB solution is injected into the TREF columnby the auto-injection system of the Waters 2000CV instrument with aflowrate of ODCB set at 1 ml/min. Following the sample injection, theODCB flow is diverted away from the TREF column. As the sample is keptinside the column, the column is allowed to cool down in the oil bathfrom 140° C. down to 0° C. at the cooling rate of 1.5° C./min. In thiscooling step, the polymer molecules in the test sample are precipitatedonto the packing beads in the TREF column. While the column is still at0° C. temperature, a flow of hot ODCB at 1 ml/min is re-introduced tothe TREF column for 2 minutes to elute the soluble fraction of thepolymer sample and detected by the IR detector set at 3.4 micrometerwavelength. Then, the temperature is raised at a heating rate of 2°C./min while the ODCB flow is maintained at 1 ml/min through the TREFcolumn to elute the higher melting polymer fractions which are beingdetected on-line by the IR4 detector.

5. Melt Flow Rate (MFR)

The MFR of the samples were determined according to ISO 1133 at 230° C.Two different loads were used: 2.16 kg and 5 kg. Values are reported asMFR(230/2.16) and MFR(230/5), respectively.

6. Productivity

The productivity of a catalyst is determined by dividing the producedmass of polypropylene by the mass of catalyst used and the reactiontime.

7. Yield

The yield of a sample is determined by dividing the isolated amount ofthe desired product divided by the theoretical achievable amount of theproduct.

The following abbreviations are employed:

PP=polypropylene

MC=metallocene

Cat=supported catalyst system

h=hour

XS=Xylene Soluables

Synthesis of Metallocenes Example 1Dimethylsilanediylbis(2-methyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride 4,7-Dibromo-2-methyl-indan-1-one

94.37 g (0.40 mol) 1,4-Dibromobenzene and 106.7 g (0.80 mol) anhydrousaluminum trichloride were placed in a 1000 ml round bottom flaskequipped with a mechanical stirrer. 62.72 g (0.60 mol) 2-Methyl-acryloylchloride were added under heat evolution (50-55° C.). The mixture washeated, starting at 105° C. a strong gas evolution was observed and thetemperature rose to 135° C. Heating of the now solid mass was continuedfor 3 h at 110° C. After cooling to room temperature 200 g ice was addedvery carefully, followed by the careful addition of 200 ml cone. HCl.The mixture was extracted three times with 250 ml dichloromethane each.The combined organic layers were washed with 250 ml water and 250 ml ofa saturated sodium bicarbonate solution, dried over magnesium sulfate,and the solvent was removed in vacuo. Flash chromatography using silicaand heptane/dichloromethane (1:2) yielded 19.3 g (63 mmol, 16%) of thedesired indanone as a white solid. ¹H-NMR (500 MHz, CDCl3): δ=7.67, 7.54(2×d, 2H, aromatic), 3.30 (m, 1H, COCHCH3), 2.74-2.64 (m, 2H, benzylic),1.30 (d, 3H, CH₃) ppm.

4,7-Dibromo-2-methyl-1H-indene

In a 250 ml round bottom flask 19.2 g (63 mmol)4,7-Dibromo-2-methyl-indan-1-one were dissolved in 70 ml of toluene at50° C. Then 2.63 g (1.1 eq.) sodium borohydride were added. At 50° C. 11ml (4.3 eq.) methanol were added dropwise over a period of 30 min.Stirring was continued at 50° C. for 3 h (complete conversion) and then50 ml water and 50 ml of 2M H₂SO₄ were added. The aqueous phase wasextracted 2 times with 100 ml toluene. The combined organic layers werewashed with 50 ml 2M H₂SO₄ and 50 ml of a sodium chloride solution,dried over magnesium sulfate and the solvent was removed in vacuo. 200ml toluene and 200 mg p-toluene sulfonic acid were added and thesolution was heated on a Dean-Stark-trap for 90 min. 50 ml of asaturated sodium bicarbonate solution were added. The aqueous layer wasextracted 2 times with 50 ml toluene each. The combined organic layerswere washed with 50 ml of a saturated sodium bicarbonate solution and 50ml of a sodium chloride solution, dried over magnesium sulfate and thesolvent was removed in vacuo to yield 17.8 g (62 mmol, 98%) of thedesired indene as a slightly brown oil. ¹H-NMR (500 MHz, CDCl3): δ=7.48,7.35 (2×d, 2H, aromatic), 6.49 (s, 1H, indenyl-C═CH), 3.32 (s, 2H,benzylic), 2.12 (2, 3H, CH₃) ppm.

4,7-Bis-(4-t-butyl-phenyl)-2-methyl-1H-indene

In a 250 ml roundbottom flask were placed 7.7 g (26.8 mmol)4,7-Dibromo-2-methyl-1H-indene, 12.0 g (2.5 eq.) t-butylphenyl boronicacid, 120 mg (2 mol %) palladium acetate, 18.76 g (134.4 mmol) potassiumcarbonate, 17.24 g (53.5 mmol) tetrabutylammonium bromide, 74 mldegassed water and 74 ml degassed toluene. The mixture was stirred for18 h at 76° C. After cooling to room temperature, 50 ml toluene and 50ml water were added. The aqueous phase was extracted 3 times with 50 mltoluene. The combined organic layers were washed once with 100 ml of 2Msodium hydroxide solution and 3 times with 50 ml water each, and driedover magnesium sulfate. Removal of the solvent in vacuo and purificationvia flash chromatography on silica using heptane/dichloromethane (20:1)yielded 8.14 g (20.6 mmol, 77%) of the desired indene as a white solid.¹H-NMR (500 MHz, CDCl₃): δ=7.57-7.36 (m, 10H, aromatic), 6.70, 6.57(2×s, 1H, indenyl-C═CH), 3.41 (“d”, 2H, benzylic), 2.15 (2×s, 3H, CH₃),1.37, 1.35 (2×s, 18H, C(CH₃)₃) ppm.

Bis-[4,7-bis-(4-t-butyl-phenyl)-2-methyl-1H-inden-1-yl]-dimethyl-silane

In a flame dried 250 ml roundbottom flask 7.45 g (18.9 mmol)4,7-Bis-(4-t-butyl-phenyl)-2-methyl-1H-indene were dissolved 127 mltoluene and 7.45 ml THF. 7.93 ml (1.05 eq., 2.5 M in toluene) n-Butyllithium were added dropwise at room temperature and the solution washeated to 80° C. for 1 h. After cooling to 50° C., 1.22 g (0.5 eq.)dimethyldichlorosilane were added and the reaction mixture was stirredfor 17 h at 60° C. The mixture was given to 100 ml water. The aqueousphase was extracted 3 times with 50 ml toluene each and the combinedorganic layers were washed with 50 ml water and 50 ml of a saturatedsodium chloride solution, and dried over magnesium sulphate. Removal ofthe solvent in vacuo and chromatography on silica usingheptane/dichloromethane (10:1) as the eluent afforded 5.7 g (6.7 mmol,71.4%) of the ligand as a slightly offwhite oil. ¹H-NMR (500 MHz,CDCl₃): δ=7.68-7.21 (m, 20H, aromatic), 6.84, 6.79 (1×d, 1×s, 2H,indenyl-C═CH), 3.85, 3.59 (1×m, 1×s, 2H, benzylic), 2.26, 2.19, 2.16,2.15 (4×s, 6H, CH₃), 1.37-1.26 (m×s, 36H, C(CH₃)₃), 0.41, 0.27, 0.09,−0.11, −0.13 (5×s, 6H, Si(CH₃)₂) ppm.

Dimethylsilanediylbis(4,7-bis-(4-t-butyl-phenyl)-2-methyl-1-indenyl)zirconiumdichloride

In a flame dried 100 ml roundbottom flask 3.8 g (4.5 mmol)Bis-[4,7-bis-(4-t-butyl-phenyl)-2-methyl-1H-inden-1-yl]-dimethyl-silanewere dissolved in 38 ml diethyl ether and 3.7 ml (2.05 eq., 2.5 M intoluene) n-butyl lithium were added at room temperature. After stirringovernight, 1.1 g (4.7 mmol) zirconium tetrachloride was added inportions. Stirring was continued for 5 h and the solid was isolated byfiltration and washing twice with 15 ml diethyl ether each. The solidwas extracted with 100 ml dichloromethane. Removal of the solvent invacuo yielded 1.2 g (1.2 mmol, 27%) of the racemic complex. ¹H-NMR (500MHz, CDCl₃): δ=7.80 (s, 2H, aromatic), 7.63, 7.51, 7.44 (3×m, 18H,aromatic), 6.99 (s, 2H, indenyl-C═CH), 2.31 (s, 6H, CH₃), 1.37 (s, 6H,Si(CH₃)₂), 1.36, 1.32 (2×s, 36H, C(CH₃)₃) ppm.

Example 2Dimethylsilanediylbis(2-methyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride 4,7-Bis-(1-naphthyl)-2-methyl-1H-indene

In a 500 ml roundbottom flask were placed 17.6 g (61.1 mmol)4,7-Dibromo-2-methyl-1H-indene, 26.3 g (2.5 eq.) 1-napthyl boronic acid,274 mg (2 mol %) palladium acetate, 42.23 g (2.5 eq.) potassiumcarbonate, 39.4 g (2 eq.) tetrabutylammonium bromide, 169 ml degassedwater and 169 ml degassed toluene. The mixture was stirred under refluxfor 20 h. After cooling to room temperature, 100 ml toluene and 100 mlwater were added. The aqueous phase was extracted 3 times with 100 mltoluene. The combined organic layers were washed once with 100 ml of 2Msodium hydroxide solution and 3 times with 50 ml water each, and driedover magnesium sulfate. Removal of the solvent in vacuo and purificationvia flash chromatography on silica using heptane/dichloromethane (10:1)yielded 15.3 g (40 mmol, 65%) of the desired indene as a white solid.¹H-NMR (500 MHz, CDCl₃): δ=8.11, 7.89-7.77, 7.57-7.26 (3×m, 16H,aromatic), 6.61, 6.18 (2×s, 1H, indenyl-C═CH), 3.49 (“d”, 2H, benzylic),2.09 (2×s, 3H, CH₃) ppm.

Bis-[4,7-bis-(1-naphthyl)-2-methyl-1H-inden-1-yl]-dimethyl-silane

In a flame dried 250 ml roundbottom flask 2.0 g (5.2 mmol)4,7-Bis-(1-naphthyl)-2-methyl-1H-indene were dissolved 34 ml toluene and2 ml THF. 2.2 ml (1.05 eq., 2.5 M in toluene) n-Butyl lithium were addeddropwise at room temperature and the solution was heated to 80° C. for 1h. After cooling to 50° C., 337 mg (0.5 eq.) dimethyldichlorosilane wereadded and the reaction mixture was stirred for 17 h at 60° C. Themixture was given to 100 ml water. The aqueous phase was extracted 3×with 50 ml toluene each and the combined organic layers were washed with50 ml water and 50 ml of a saturated sodium chloride solution, and driedover magnesium sulphate. Removal of the solvent in vacuo andchromatography on silica using heptane/dichloromethane (10:1) as theeluent afforded 1.8 g (2.2 mmol, 84%) of the ligand as a slightlyoffwhite oil. ¹H-NMR (500 MHz, CDCl₃): =8.08-7.29 (m, 32H, aromatic),6.35, 6.26 (2×d, 2H, indenyl-C═CH), 4.04-3.94 (m, 2H, benzylic),2.24-2.15 (m, 6H, CH₃), 0.00, −0.01, −0.02, −0.03, −0.04 (5×s, 6H,Si(CH₃)₂) ppm.

Dimethylsilanediylbis(4,7-bis-(1-naphthyl)-2-methyl-1-indenyl)zirconiumdichloride

In a flame dried 100 ml roundbottom flask 1.8 g (2.2 mmol)Bis-[4,7-bis-(1-naphthyl)-2-methyl-1H-inden-1-yl]-dimethyl-silane weredissolved in 18 ml diethyl ether and 1.8 ml (2.05 eq., 2.5 M in toluene)n-butyl lithium were added at room temperature. After stirringovernight, 536 mg (2.3 mmol) zirconium tetrachloride was added inportions. Stirring was continued for 2 h and the solvent was removed invacuo. 30 ml toluene and 1.8 ml THF were added and the mixture wasstirred for 4 h at 75° C. The solvent was removed and the complex wasisolated by extraction with toluene to yield 430 mg (0.44 mmol, 20%) ofthe racemic complex. ¹H-NMR (500 MHz, CDCl₃): δ=8.04-7.11 (m, 32H,aromatic), 6.65 (s, 2H, indenyl-C═CH), 2.21 (s, 6H, CH₃), 1.27 (s, 6H,Si(CH₃)₂) ppm.

Comparative Example 3 Bis(2,4,7-trimethyl-1H-inden-1-yl)-dimethyl-silaneBis(2,4,7-trimethyl-1H-inden-1-yl)-dimethyl-silane

10.6 ml (26.5 mmole) of a 2.5 M n-butyl lithium solution in hexane wereadded to a solution of 4.2 g (26.5 mmole) of 2,4,7-trimethylindene in 50ml of tetrahydrofuran at 0° C. and the mixture was heated under refluxfor a further hour and then added to a solution of 3.42 g ofdimethyldichlorosilane in 12 ml of tetrahydrofuran at room temperature.The red suspension was stirred at room temperature for 4 hours and washeated under reflux for additional 4 hours. The mixture was poured ontoice and extracted with diethylether. The combined organic phases weredried over sodium sulfate and evaporated to dryness. Recrystallizationfrom hexane yielded 3.95 g (10.6 mmole) ofBis(2,4,7-trimethyl-1H-inden-1-yl]-dimethylsilane.

Comparative Example 4Dimethylsilanediylbis(2,4,7-trimethyl-indenyl)-zirconiumdichlorideDimethylsilanediylbis(2,4,7-trimethyl-indenyl)-zirconiumdichloride

Continuing with the product produced in Comparative Example 3, 4.32 ml(10.8 mmole) of a 2.5 M n-butyl lithium solution in hexane were added toa solution of 2.0 g (5.4 mmole) ofBis(2,4,7-trimethyl-1H-inden-1-yl]-dimethylsilane in 40 ml ofdiethylether at 0° C. The mixture was stirred at room temperature for 2hours and concentrated to 25 ml and the precipitate was filtered over aG4 frit. After being washed with hexane the dilithium salt was added to1.26 g (5.4 mmole) of zirconiumtetrachloride in 25 ml of methylenechloride at −78° C. The solvent was removed in vacuum resulting in acrude metallocene with a rac:meso ratio of 1:1. Purification andrac:meso separation was accomplished by fractional crystallisation frommethylenehloride/hexane.

Preparation of Methylaluminoxane Treated Silica Example 5

To a stirred suspension of 293 g of silica (Grace XPO2107, dried at 180°C. and 1 mbar for 16 hours, LOD<0.5 wt % and LOI=2.6 wt %) in 1500 mL oftoluene is added slowly 300 mL of a 30 wt-% solution ofmethylaluminoxane in toluene (Albemarle Corporation) at roomtemperature. During the addition the temperature must not exceed 30° C.After the addition is complete, the mixture is stirred for two hours atroom temperature and separated by filtration. The residue is washed withtwo 1500 mL portions of toluene and three 1500 mL portions of isohexaneand dried in vacuum to constant weight. The methylaluminoxane treatedsilica is obtained as a free-flowing powder in a yield of 408 g.

Preparation of Supported Metallocene Catalysts Example 6

10.0 g of the methylaluminoxane treated silica prepared in Example 5 areplaced in a fitted glass filter as a column with a smooth surface. Aminimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 361 mg ofDimethylsilanediylbis(2-methyl-4,7-bis-(4-t-butyl-phenyl)-1-indenyl)zirconiumdichloride (prepared in Example 1) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 11.8 g.

Example 7

10.0 g of the methylaluminoxane treated silica prepared in Example 5 areplaced in a flitted glass filter as a column with a smooth surface. Aminimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 353 mg ofDimethylsilanediylbis(2-methyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride (prepared in Example 2) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing reddish powder in a yield of 11.5 g.

Comparative Example 8

10.0 g of the methylaluminoxane treated silica prepared in Example 12are placed in a fritted glass filter as a column with a smooth surface.A minimal amount of toluene is added and the treated silica is carefullystirred with a spatula to remove any air pockets in the column. Theexcess toluene is removed by filtration leaving a smooth surface. In aseparate flask 191 mg ofDimethylsilanediylbis(2,4,7-trimethyl-indenyl)-zirconiumdichloride(prepared in Comparative Example 4) are mixed with 27 mL of toluene and13.6 mL of a 30 wt-% solution of methylaluminoxane in toluene (AlbemarleCorporation). The slurry is stirred at room temperature for one hour togive an orange solution. This solution is then carefully added on top ofthe methylaluminoxane treated silica and slowly filtered off withinapproximately 30 minutes. When the surface of the colored solutionreaches the top of the silica, the filtration process is stopped and thefilter cake is carefully and thoroughly stirred by means of a spatula.The catalyst is then allowed to rest for one hour. The residual solventis filtered off and the catalyst is washed twice with isohexane (20 mL)and dried in a nitrogen purge to constant weight. The catalyst isobtained as free-flowing orange powder in a yield of 11.5 g.

Polymerizations Polymerization Procedure (Batch Propylene Homo- andCo-Polymerization)

A dry and nitrogen purged 5 dm³ autoclave equipped with a stirrer ischarged with if desired 100 g of metallocene polymer seed bed.Optionally, a certain amount of hydrogen is metered in.Triisobutylaluminum (1 cm³ of a 10 wt.-% solution in heptane), liquidpropylene (one-half of the total amount used for the run), andoptionally, a certain amount of ethylene are metered in and the mixtureis stirred for at least 5 minutes (stirrer speed 200 rpm) at 20° C. Thensupported metallocene catalyst, suspended in 5 cm³ of white oil, isinjected with liquid propylene (one-half of total amount used for therun). The reactor is heated to the internally measured run temperature(65, 60 or 30° C.) within 11 minutes. The polymerization reaction isallowed to proceed at the run temperature for either 15 or 60 minutes.During the 60 min copolymerization runs the reactor pressure wasmaintained by continuous feeding of ethylene and propylene. Thepolymerization is stopped by releasing the monomer and cooling down thereactor. The polymer is discharged and dried under reduced pressure.

The following examples were carried out according to the polymerizationprocedure described above:

TABLE 1 Polymerizations Catalyst Polym. Polym. Productivity Poly. FromH2 C3 C2 Catalyst Temp. Time Yield [g polymer/g Example Example [mg] [g][g] [mg] [° C.] [min] [g] catalyst*hour] 1 6 — 1830 — 68 65 60 119 17502 6 50 1834 — 52 65 60 692 13300 3 6 10 1836 20 75 65 60 210 2800 4 6 101767 60 75 65 60 233 3100 5 7 — 1838 — 110 65 60 132 1200 6 7 50 1834 —56 65 60 532 9500 7 7 10 1756 20 60 65 60 117 1950 8 7 10 1780 60 60 6560 172 2870 9 8 — 1836 — 60 65 60 62 1033 10 8 50 1832 — 58 65 60 4127100 11 8 10 1820 20 62 65 60 90 1450 12 8 10 1824 60 60 65 60 107 1780

TABLE 2 Polymer Properties Catalyst MFR Poly. from C2 Tm 2.16 Mw XSExample Example [wt %] [deg C.] [g/10′] [kg/mol] Mw/Mn [wt %] 1 6 — 1470.2 817 2.3 1.4 2 6 — 149 16.3 207 2.3 1.1 3 6 2.2 135 8.5 289 2.0 1.4 46 5.2 113 10.0 237 2.2 1.6 5 7 — 147 0.01 1420 2.4 1.4 6 7 — 148 3.3 3302.5 1.1 7 7 2.5 130 5.9 309 2.7 1.4 8 7 5.5 111 7.9 295 2.5 1.7 9 8 —144 out of 73 2.6 n.d measureable range 10 8 — 146 out of 19 2.7 n.dmeasureable range 11 8 Sticky waxy material 12 8 Sticky waxy materialAnalysis of Results

Table 1 and Table 2 represent the raw data presented by test run; theremaining tables 3-break that data out by the ratio of propylene toethylene (or if it is a propylene homo polymer) and whether hydrogen wasused in the polymerization process.

Propylene Homo Polymers

Analysis 1: Production of Propylene Homo Polymers without the Use ofHydrogen.

Table 3 shows the results of two experimental Metallocene catalystsconforming to the requirements of the invention compared to acomparative example.

The individual catalyst comparisons between inventive examples 1 and 5and comparative example 9 substantiate the outstanding improvements overthe state of the art. When examples 1 and 5 are compared to comparativeexample 9, the inventive examples exhibit significantly lower MFR 2.16rates and increases in Molecular Weight and Polymer Melting Point(T_(m)). Specifically for MFR 2.16, the inventive examples 1 and 5 showMFR values of less than 0.2 while the MFR of the polymer produced in thecomparative example 9 is so high that the MFR was out of range and wasnot measureable. For the Polymer Melting Point (T_(m)), the inventiveexamples 1 and 5 show a respective increase of 3° C. over the originalvalue. For the molecular weight, the inventive examples 1 and 5 show arespective increase of more than 10 to 20 fold over the original value.This dramatic increase of Molecular Weight opens full access toapplication fields like film, pipe or sheets, where a high MolecularWeight is mandatory. Even more surprisingly is that the inventiveexamples showed these dramatic improvements in product properties atmuch higher productivity levels. Inventive example 1 shows a 69%increase in productivity and inventive example 5 shows a 16% increase inproductivity over the original value.

Analysis 2: Production of Propylene Homo Polymers with the Use ofHydrogen.

Table 4 shows the results of two experimental Metallocene catalystsconforming to the requirements of the invention compared to acomparative example.

The individual catalyst comparisons between inventive examples 2 and 6and comparative example 10 again substantiate the outstandingimprovements over the state of the art. When examples 2 and 6 arecompared to comparative example 10, the inventive examples exhibitsignificantly lower MFR 2.16 rates and increases in Molecular Weight andPolymer Melting Point (T_(m)). Specifically for MFR 2.16, the inventiveexamples 2 and 6 show MFR values of less than 16.3 while the MFR of thepolymer produced in the comparative example 10 is so high that the MFRwas out of range and was not measureable. For the Polymer Melting Point(T_(m)), the inventive examples 2 and 6 show a respective increase of 2to 3° C. over the original value. For the molecular weight, theinventive examples 2 and 6 show a respective increase of more than 10 to17 fold over the original value. This dramatic increase of MolecularWeight opens full access to application fields like film, fibre andinjection moulding, where a Molecular Weight in the achieved range ismandatory. Even more surprisingly is that the inventive examples showedthese dramatic improvements in product properties at much higherproductivity levels. Inventive example 2 shows a 87% increase inproductivity and inventive example 6 shows a 34% increase inproductivity over the original value.

Propylene/Ethylene Co-Polymers

The polymerization performance and the properties of products made fromthe inventive catalysts were tested at two levels of anethylene/propylene mix to form co-polymers (Table 5). In each case theinventive catalysts from examples 6 and 7 have been tested, and comparedagainst the comparative catalyst from example 8.

Analysis 3: Production of Propylene/Ethylene Co-Polymers with aPropylene/Ethylene Ratio of Approximately 90 and 30 (20 g Resp. 60 g ofEthylene) in the Presence of Hydrogen.

Two inventive catalyst (examples 3, 4 and 7, 8) have tested against thecomparative catalyst, (examples 11, 12), the results being presented inTable 5. As before, the inventive catalyst showed significantimprovements over the comparative catalyst. Under the applied standardconditions for testing random co-polymers and using the comparativecatalyst it was no longer possible to produce a polymer! The productisolated from the polymerisation was a waxy and sticky material. As aconsequence, such a catalyst can not be commercially used. Specificallyfor MFR 2.16, the inventive examples 3, 4 and 7, 8 show MFR values ofstill less than 10 while the MFR of the waxes (as indicated above, thematerial was no longer a polymer!) produced in the comparative examples11 and 12 was so high that the MFR was out of range and was notmeasureable. For the molecular weight, the inventive examples 3, 4 and7, 8 show still values above 230 kg/mol which open full access toapplication fields like high transparent film, fibre and hightransparent injection moulding. Even more surprisingly is that theinventive examples showed these dramatic improvements in productproperties at much higher productivity levels. Inventive examples 3 and7 where 20 g of ethylene was used in the polymerization show a 93% and34% increase in productivity over the directly comparable value ofexample 11 and inventive examples 4 and 8 where 60 g of ethylene wasused show a 74% and 61% increase in productivity over the directlycomparable value of example 12.

While the above description contains many specifics, these specificsshould not be construed as limitations of the invention but merely aspreferred embodiments thereof. Those skilled in the art will envisionmany other embodiments within the scope and spirit of the claims asdefined by the claims appended hereto.

TABLE 3 Production of propylene homo polymers without the use ofhydrogen Catalyst Polym. Polym. Productivity MFR Poly. From H2 C3 C2Catalyst Temp. Time Yield [g polymer/g Tm 2.16 Mw XS Example Example[mg] [g] [g] [mg] [° C.] [min] [g] catalyst*hour] [deg C.] [g/10′][kg/mol] Mw/Mn [wt %] 1 6 — 1830 — 68 65 60 119 1750 147 0.2 817 2.3 1.45 7 — 1838 — 110 65 60 132 1200 147 0.01 1420 2.4 1.4 9 8 — 1836 — 60 6560 62 1033 144 out of 73 2.6 n.d measureable range

TABLE 4 Production of propylene homo polymers with the use of hydrogenCatalyst Polym. Polym. Productivity MFR Poly. From H2 C3 C2 CatalystTemp. Time Yield [g polymer/g Tm 2.16 Mw XS Example Example [mg] [g] [g][mg] [° C.] [min] [g] catalyst*hour] [deg C.] [g/10′] [kg/mol] Mw/Mn [wt%] 2 6 50 1834 — 52 65 60 692 13300 149 16.3 207 2.3 1.1 6 7 50 1834 —56 65 60 532 9500 148 3.3 330 2.5 1.1 10 8 50 1832 — 58 65 60 412 7100146 out of 19 2.7 n.d measureable range

TABLE 5 Production of propylene/ethylene co-polymers with apropylene/ethylene ratio of approximately 90 and 30 (20 g resp. 60 g ofethylene) in the presence of hydrogen Produc- tivity [g Catalyst Polym.Polym. polymer/g MFR Poly. From H2 C3 C2 Catalyst Temp. Time Yieldcatalyst* C2 Tm 2.16 Mw XS Example Example [mg] [g] [g] [mg] [° C.][min] [g] hour] [wt %] [deg C.] [g/10′] [kg/mol] Mw/Mn [wt %] 3 6 101836 20 75 65 60 210 2800 2.2 135 8.5 289 2.0 1.4 4 6 10 1767 60 75 6560 233 3100 5.2 113 10.0 237 2.2 1.6 7 7 10 1756 20 60 65 60 117 19502.5 130 5.9 309 2.7 1.4 8 7 10 1780 60 60 65 60 172 2870 5.5 111 7.9 2952.5 1.7 11 8 10 1820 20 62 65 60 90 1450 Sticky waxy material 12 8 101824 60 60 65 60 107 1780 Sticky waxy material

1. A catalyst composition comprising a metallocene compound havingformula 1:

in which: M¹ is a metal of the Groups 4-6 of the Periodic Table of theElements, R¹ and R² are identical or different and are each a hydrogenatom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy groupof from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, analkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogenatom, or a NR₂ ³² group, where R³² is an alkyl group of from 1 to about10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms andR¹ and R² may form one or more ring system(s), R³ and R^(3′) areidentical or different and are each a halogen atom, or a linear, cyclicor branched hydrocarbon group which may optionally be halogenated and/ormay contain one or more hetero atoms selected from Si, B, Al, O, S, Nand P, said hydrocarbon group being selected from an alkyl group of from1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, analkylarylalkenyl group of from 9 to about 40 carbon atoms, an arylalkylgroup of 7 to 20 carbon atoms, an alkoxy group of from 1 to about 10carbon atoms, an aryl group of from 6 to about 20 carbon atoms, aheteroaryl group of 3 to about 20 carbon atoms, an aryloxy group of from6 to about 10 carbon atoms, a silyloxy group of about 3 to 20 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms and a NR₂ ³²group, where R³² is an alkyl group of from 1 to about 10 carbon atoms oran aryl group of from 6 to about 14 carbon atoms, R⁴ and R^(4′) areidentical or different and are each a hydrogen atom, a halogen atom, ora linear, cyclic or branched hydrocarbon group which may be halogenatedand/or may contain one or more hetero atoms selected from Si, B, Al, O,S, N and P, said hydrocarbon group being selected from an alkyl group offrom 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 toabout 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbonatoms, or an alkylarylalkenyl group of from 9 to about 40 carbon atoms,an arylalkyl group of 7 to 20 carbon atoms, an alkoxy group of from 1 toabout 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms,a heteroaryl group of 3 to about 20 carbon atoms, an aryloxy group offrom 6 to about 10 carbon atoms, a silyloxy group of about 3 to 20carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, ahalogen atom and a NR₂ ³² group, where R³² is an alkyl group of from 1to about 10 carbon atoms or an aryl group of from 6 to about 14 carbonatoms, R⁵, R^(5′), R⁸ and R^(8′) are identical or different and are eachan aryl group of from 6 to about 40 carbon atoms, an alkylaryl group offrom 7 to about 40 carbon atoms, an alkenylaryl group of from 8 to about40 carbon atoms, a substituted or unsubstituted silylaryl group, or an(alkyl)(silyl)aryl group, and optionally may be halogenated and/or maycontain one or more hetero atoms selected from Si, B, Al, O, S, N and P,R⁶, R^(6′), R⁷ and R^(7′) are identical or different and are each ahydrogen atom, a halogen, or a linear, cyclic or branched hydrocarbongroup which may optionally be halogenated and/or may contain one or morehetero atoms selected from Si, B, Al, O, S, N and P, wherein thehydrocarbon group is selected from an alkyl group of from 1 to about 20carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms,an alkylaryl group of from 7 to about 40 carbon atoms, analkylarylalkenyl group of from 9 to about 40 carbon atoms, an arylalkylgroup of 7 to 20 carbon atoms, an alkoxy group of from 1 to about 10carbon atoms, an aryl group of from 6 to about 20 carbon atoms, aheteroaryl group of 3 to about 20 carbon atoms, an aryloxy group of from6 to about 10 carbon atoms, a silyloxy group of about 3 to 20 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, a halogenatom and a NR₂ ³² group, where R³² is an alkyl group of from 1 to about10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, R¹⁰is a bridging group wherein R¹⁰ is selected from:

where R⁴⁰ and R⁴¹, even when bearing the same index, can be identical ordifferent and are each a hydrogen atom, or a hydrocarbon group which mayoptionally be halogenated or which may contain hetero atoms selectedfrom Si, B, Al, O, S, N and P, wherein the hydrocarbon group is selectedfrom an alkyl group having from 1 to about 30 carbon atoms, an arylgroup of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an arylalkyl group of from 7to about 40 carbon atoms, an alkylaryl group of from 7 to about 40carbon atoms, a substituted or unsubstituted alkylsilyl,alkyl(aryl)silyl group, an arylsilyl group or an arylalkenyl group offrom 8 to about 40 carbon atoms, or wherein R⁴⁰ and R⁴¹ together withthe atoms connecting them can form one or more cyclic systems, x is aninteger from 1 to 18, M¹² is silicon, germanium or tin, and R¹⁰ may alsolink two units of the formula 1 to one another.
 2. The catalystcomposition of claim 1 wherein: M¹ is a metal of the Group 4 of thePeriodic Table of the Elements, R¹ and R² are identical or different andare each an alkyl group of from 1 to about 10 carbon atoms, an alkoxygroup of from 1 to about 10 carbon atoms, an aryloxy group of from 6 toabout 10 carbon atoms or a halogen atom, or R¹ and R² together may formone or more ring system(s), R³ and R^(3′) are identical or different andare each a halogen atom or a linear, cyclic or branched hydrocarbongroup which may optionally be halogenated and/or may optionally containone or more hetero atoms selected from Si, B, Al, O, S, N and P, whereinthe hydrocarbon group is selected from an alkyl group of from 1 to about10 carbon atoms, an alkylalkenyl group of from 3 to about 10 carbonatoms, an alkylaryl group of from 7 to about 20 carbon atoms, analkylarylalkenyl group of from 9 to about 20 carbon atoms, an arylalkylgroup of 7 to 15 carbon atoms, an alkoxy group of from 1 to about 6carbon atoms, an aryl group of from 6 to about 10 carbon atoms, aheteroaryl group of 3 to about 10 carbon atoms, an aryloxy group of from6 to about 10 carbon atoms, a silyloxy group of about 3 to 10 carbonatoms, an alkenyl group of from 2 to about 6 carbon atoms and a NR₂ ³²group where R³² is an alkyl group of from 1 to about 10 carbon atoms oran aryl group of from 6 to about 10 carbon atoms, R⁴ and R^(4′) areidentical or different and are each a hydrogen atom, or an alkyl groupof from 1 to about 20 carbon atoms which may optionally be halogenatedand/or may optionally contain one or more hetero atoms selected from Si,B, Al, O, S, N and P, R⁵, R^(5′), R⁸ and R^(8′) are identical ordifferent and are each an aryl group of from 6 to about 40 carbon atoms,an alkylaryl group of from 7 to about 40 carbon atoms, and mayoptionally contain one or more hetero atoms selected from B, Al, O, S,N, P, F, Cl and Br, R⁶, R^(6′), R⁷ and R^(7′) are identical or differentand are each a hydrogen atom, or an alkyl group of from 1 to about 20carbon atoms which may be halogenated and/or may contain one or morehetero atoms selected from B, Al, O, S, N and P, R¹⁰ is R⁴⁰R⁴¹Si═,R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ areidentical or different and are each a hydrogen atom, a hydrocarbon groupof from 1 to about 30 carbon atoms, in particular an alkyl group of from1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbonatoms, an arylalkyl group of from 7 to about 14 carbon atoms, or analkylaryl group of from 7 to about 14 carbon atoms.
 3. The catalystcomposition of claim 1 wherein: M¹ is zirconium, R¹ and R² are identicaland are methyl, chlorine or phenolate, R³ and R^(3′) are identical andare a linear, cyclic or branched hydrocarbon group selected from methyl,ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, t-butyl,t-butyl-methyl, i-butyl, s-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, cyclopropyl-methyl, cyclopentyl, cyclopentyl-methyl,cyclohexyl, cyclohexyl-methyl, (1-adamantyl)methyl, (2-adamantyl)methyl,benzyl, phenylethyl and phenyl-propyl, R⁴ and R^(4′) are identical andare each a hydrogen atom, R⁵, R^(5′), R⁸ and R^(8′) are identical andare each an aryl group of from 6 to about 20 carbon atoms, selected fromphenyl, 1-naphthyl, 2-naphtyl, an alkylaryl group of from 7 to about 40carbon atoms which may optionally contain one or more hetero atomsselected from B, Al, O, S, N, P, F, Cl and Br, the alkylaryl group beingselected from 4-methyl-phenyl, 4-ethyl-phenyl, 4-i-propyl-phenyl,4-t-butyl-phenyl, 3,5-dimethylphenyl, 3,5-di-t-butyl-4-methoxy-phenyl,and 2,3,4,5,6-pentafluorophenyl, R⁶, R^(6′), R⁷ and R^(7′) are identicaland are each a hydrogen atom, the bridging unit R¹⁰ is R⁴⁰R⁴¹Si═ orR⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl,naphthyl, benzyl, or 3,3,3-trifluoropropyl.
 4. The catalyst compositionof claim 1 wherein, M¹ is zirconium, R¹ and R² are identical and aremethyl or chlorine, R³ and R^(3′) are identical and are each methyl,n-heptyl, n-octyl, n-nonyl, n-decyl, cyclohexyl-methyl, t-butyl-methyl,(1-adamantyl)methyl, (2-adamantyl)methyl, benzyl, phenethyl orphenyl-propyl, R⁴ and R^(4′) are identical and are each a hydrogen atom,R⁵, R^(5′), R⁸ and R^(8′) are identical and are each phenyl, 1-naphthyl,2-naphtyl, 4-methyl-phenyl, 4-ethyl-phenyl, 4-i-propyl-phenyl,4-t-butyl-phenyl, 3,5-dimethylphenyl, 3,5-di-t-butyl-4-methoxy-phenyl,2,3,4,5,6-pentafluorophenyl, R⁶, R^(6′), R⁷ and R^(7′) are identical andare each a hydrogen atom the bridging unit R¹⁰ is R⁴⁰R⁴¹Si═ orR⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl,naphthyl, benzyl, or 3,3,3-trifluoropropyl.
 5. The catalyst compositionof claim 1 further including an aluminoxane, a Lewis acid or an ioniccompound capable of converting the metallocene compound to a cationiccompound.
 6. The catalyst composition of claim 5 wherein the aluminoxaneis a compound having the general formula selected from one of formulas6, 7, 8, or 9:

wherein radicals R in the formulas (6), (7), (8) and (9) can beidentical or different and are each an alkyl group of from 1 to about 6carbon atoms, an aryl group of from 6 to about 18 carbon atoms, benzylor hydrogen, and p is an integer from 2 to
 50. 7. The catalystcomposition of claim 5 wherein the Lewis acid is a compound havingformula 10:M²X¹X²X³  (Formula 10) where M² is B, Al or Ga, and X¹, X² and X³ arethe same or different and each are a hydrogen atom, an alkyl group offrom 1 to about 20 carbon atoms, an aryl group of from 6 to about 15carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each havingfrom 1 to 10 carbon atoms in the alkyl radical and from 6-20 carbonatoms in the aryl radical or fluorine, chlorine, bromine or iodine. 8.The catalyst composition of claim 7 wherein the Lewis acid comprises oneor more compounds selected from the group consisting oftrimethylaluminum, triethylaluminum, triisobutylaluminum,tributylaluminum, trifluoroborane, triphenylborane,tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane,tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane,tris(penta-fluorophenyl)borane, tris(tolyl)borane,tris(3,5-dimethyl-phenyl)borane, tris(3,5-difluorophenyl)borane andtris(3,4,5-trifluorophenyl)borane.
 9. The catalyst composition of claim5 wherein the ionic compound comprises one or more compound selectedfrom the group consisting of: triethylammoniumtetra(phenyl)borate,tributylammoniumtetra(phenyl)borate,trimethylammoniumtetra(tolyl)borate, tributylammoniumtetra(tolyl)borate,tributylammoniurntetra(pentafluorophenyl)borate,tributylammoniumtetra(pentaffluorophenyl) aluminate,tripropylammoniumtetra(dimethylphenyl)borate,tributylammoniumtetra(trifluoromethylphenyl)borate,tributylammoniumtetra(4-fluorophenyl)borate,N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borateN,N-dimethylaniliniumtetra(phenyl)borate,N,N-diethylaniliniumtetra(phenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate,triphenylphosphoniumtetrakis(phenyl)borate,triethylphosphoniumtetrakis(phenyl)borate,diphenylphosphoniumtetrakis(phenyl)borate,tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,triphenylcarbeniumtetrakis(pentafluorophenyl)borate,triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,triphenylcarbeniumtetrakis(phenyl)aluminate,ferroceniumtetrakis(pentafluorophenyl)borate andferroceniumtetrakis(pentafluorophenyl)aluminate.
 10. The catalystcomposition of claim 5 further including a particulate porous solidsupport.
 11. The catalyst composition of claim 10 wherein theparticulate porous solid support comprises at least one materialselected from the group consisting of silicon dioxide, aluminum oxide,aluminosilicates, zeolites, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, ThO₂, Na₂O,K₂O, LiO₂, Al/Si oxides, Mg/Al oxides, Al/Mg/Si oxides, Na₂CO₃, K₂CO₃,CaCO₃, MgCl₂, Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂ and Al(NO₃)₃,polyethylene, polypropylene, polybutene, polystyrene,divinylbenzene-crosslinked polystyrene, polyvinyl chloride,acrylonitrile-butadiene-styrene copolymer, polyamide, polymethacrylate,polycarbonate, polyester, polyacetal and polyvinyl alcohol.
 12. A methodfor olefin polymerization comprising contacting one or more olefins eachhaving from 2 to about 20 carbon atoms under olefin polymerizationreaction conditions with a catalyst system including a bridgedmetallocene component having the general formula 1,

in which: M¹ is a metal of the Groups 4-6 of the Periodic Table of theElements, R¹ and R² are identical or different and are each a hydrogenatom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy groupof from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, analkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogenatom, or a NR₂ ³² group, where R³² is an alkyl group of from 1 to about10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms andR¹ and R² may form one or more ring system(s), R³ and R^(3′) areidentical or different and are each a halogen atom, or a linear, cyclicor branched hydrocarbon group which may optionally be halogenated and/ormay contain one or more hetero atoms selected from Si, B, Al, O, S, Nand P, said hydrocarbon group being selected from an alkyl group of from1 to about 20 carbon atoms, an alkylalkenyl group of from 3 to about 20carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, analkylarylalkenyl group of from 9 to about 40 carbon atoms, an arylalkylgroup of 7 to 20 carbon atoms, an alkoxy group of from 1 to about 10carbon atoms, an aryl group of from 6 to about 20 carbon atoms, aheteroaryl group of 3 to about 20 carbon atoms, an aryloxy group of from6 to about 10 carbon atoms, a silyloxy group of about 3 to 20 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms and a NR₂ ³²group, where R³² is an alkyl group of from 1 to about 10 carbon atoms oran aryl group of from 6 to about 14 carbon atoms, R⁴ and R^(4′) areidentical or different and are each a hydrogen atom, a halogen atom, ora linear, cyclic or branched hydrocarbon group which may be halogenatedand/or may contain one or more hetero atoms selected from Si, B, Al, O,S, N and P, said hydrocarbon group being selected from an alkyl group offrom 1 to about 20 carbon atoms, an alkylalkenyl group of from 3 toabout 20 carbon atoms, an alkylaryl group of from 7 to about 40 carbonatoms, or an alkylarylalkenyl group of from 9 to about 40 carbon atoms,an arylalkyl group of 7 to 20 carbon atoms, an alkoxy group of from 1 toabout 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms,a heteroaryl group of 3 to about 20 carbon atoms, an aryloxy group offrom 6 to about 10 carbon atoms, a silyloxy group of about 3 to 20carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, ahalogen atom and a NR₂ ³² group, where R³² is an alkyl group of from 1to about 10 carbon atoms or an aryl group of from 6 to about 14 carbonatoms, R⁵, R^(5′), R⁸ and R^(8′) are identical or different and are eachan aryl group of from 6 to about 40 carbon atoms, an alkylaryl group offrom 7 to about 40 carbon atoms, an alkenylaryl group of from 8 to about40 carbon atoms, a substituted or unsubstituted silylaryl group, or an(alkyl)(silyl)aryl group, and optionally may be halogenated and/or maycontain one or more hetero atoms selected from Si, B, Al, O, S, N and P,R⁶, R^(6′), R⁷ and R^(7′) are identical or different and are each ahydrogen atom, a halogen, or a linear, cyclic or branched hydrocarbongroup which may optionally be halogenated and/or may contain one or morehetero atoms selected from Si, B, Al, O, S, N and P, wherein thehydrocarbon group is selected from an alkyl group of from 1 to about 20carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms,an alkylaryl group of from 7 to about 40 carbon atoms, analkylarylalkenyl group of from 9 to about 40 carbon atoms, an arylalkylgroup of 7 to 20 carbon atoms, an alkoxy group of from 1 to about 10carbon atoms, an aryl group of from 6 to about 20 carbon atoms, aheteroaryl group of 3 to about 20 carbon atoms, an aryloxy group of from6 to about 10 carbon atoms, a silyloxy group of about 3 to 20 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, a halogenatom and a NR₂ ³² group, where R³² is an alkyl group of from 1 to about10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, R¹⁰is a bridging group wherein R¹⁰ is selected from:

where R⁴⁰ and R⁴¹, even when bearing the same index, can be identical ordifferent and are each a hydrogen atom, or a hydrocarbon group which mayoptionally be halogenated or which may contain hetero atoms selectedfrom Si, B, Al, O, S, N and P, wherein the hydrocarbon group is selectedfrom an alkyl group having from 1 to about 30 carbon atoms, an arylgroup of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an arylalkyl group of from 7to about 40 carbon atoms, an alkylaryl group of from 7 to about 40carbon atoms, a substituted or unsubstituted alkylsilyl,alkyl(aryl)silyl group, an arylsilyl group and an arylalkenyl group offrom 8 to about 40 carbon atoms, or wherein R⁴⁰ and R⁴¹ together withthe atoms connecting S them can form one or more cyclic systems, x is aninteger from 1 to 18, M¹² is silicon, germanium or tin, and R¹⁰ may alsolink two units of the formula 1 to one another.
 13. The method of claim12 wherein: M¹ is a metal of the Group 4 of the Periodic Table of theElements, R¹ and R² are identical or different and are each an alkylgroup of from 1 to about 10 carbon atoms, an alkoxy group of from 1 toabout 10 carbon atoms, an aryloxy group of from 6 to about 10 carbonatoms or a halogen atom, or R¹ and R² together may S form one or morering system(s), R³ and R^(3′) are identical or different and are each ahalogen atom or a linear, cyclic or branched hydrocarbon group which mayoptionally be halogenated and/or may optionally contain one or morehetero atoms selected from Si, B, Al, O, S, N and P, wherein thehydrocarbon group is selected from an alkyl group of from 1 to 0 about10 carbon atoms, an alkylalkenyl group of from 3 to about 10 carbonatoms, an alkylaryl group of from 7 to about 20 carbon atoms, analkylarylalkenyl group of from 9 to about 20 carbon atoms, an arylalkylgroup of 7 to IS carbon atoms, an alkoxy group of from 1 to about 6carbon atoms, an aryl group of from 6 to about 10 carbon atoms, aheteroaryl group of 3 to about 10 carbon atoms, an aryloxy 5 group offrom 6 to about 10 carbon atoms, a silyloxy group of about 3 to 10carbon atoms, an alkenyl group of from 2 to about 6 carbon atoms and aNR₂ ³² group where R³² is an alkyl group of from 1 to about 10 carbonatoms or an aryl group of from 6 to about 10 carbon atoms, R⁴ and R^(4′)are identical or different and are each a hydrogen atom, or an alkylgroup of from 1 to about 20 carbon atoms which may optionally behalogenated and/or may optionally contain one or more hetero atomsselected from Si, B, Al, O, S, N and P, R⁵, R^(5′), R⁸ and R^(8′) areidentical or different and are each an aryl group of from 6 to about 40carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, andmay optionally contain one or more hetero atoms selected from B, Al, O,S, N, P, F, Cl and Br, R⁶, R^(6′), R⁷ and R^(7′) are identical ordifferent and are each a hydrogen atom, or an alkyl group of from 1 toabout 20 carbon atoms which may be halogenated and/or may contain one ormore hetero atoms selected from B, Al, O, S, N and P, R¹⁰ is R⁴⁰R⁴¹Si═,R⁴⁰R⁴¹Ge═, R⁴⁰R⁴¹C═ or —(R⁴⁰R⁴¹C—CR⁴⁰R⁴¹)—, where R⁴⁰ and R⁴¹ areidentical or different and are each a hydrogen atom, a hydrocarbon groupof from 1 to about 40 carbon atoms selected from an alkyl group of from1 to about 10 carbon atoms, an aryl group of from 6 to about 40 carbonatoms, an arylalkyl group of from 7 to about 14 carbon atoms and analkylaryl group of from 7 to about 14 carbon atoms.
 14. The method ofclaim 12 wherein M¹ is zirconium, R¹ and R² are identical and aremethyl, chlorine or phenolate, R³ and R^(3′) are identical and are alinear, cyclic or branched hydrocarbon group selected from methyl,ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, t-butyl,t-butyl-methyl, i-butyl, s-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, cyclopropyl-methyl, cyclopentyl, cyclopentyl-methyl,cyclohexyl, cyclohexyl-methyl, (1-adamantyl)methyl, (2-adamantyl)methyl,benzyl, phenylethyl or phenyl-propyl, R⁴ and R^(4′) are identical andare each a hydrogen atom, R⁵, R^(5′), R⁸ and R^(8′) are identical andare each an aryl group of from 6 to about 20 carbon atoms, selected fromphenyl, 1-naphthyl, 2-naphtyl, or an alkylaryl group of from 7 to about40 carbon atoms which may optionally contain one or more hetero atomsselected from B, Al, O, S, N, P, F, Cl and Br, the alkylaryl group beingselected from 4-methyl-phenyl, 4-ethyl-phenyl, 4-i-propyl-phenyl,4-t-butyl-phenyl, 3,5-dimethylphenyl, 3,5-di-t-butyl-4-methoxy-phenyl,2,3,4,5,6-pentafluorophenyl, R⁶, R^(6′), R⁷ and R^(7′) are identical andare each a hydrogen atom, the bridging unit R¹⁰ is R⁴⁰R⁴¹Si═ orR⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl,naphthyl, benzyl, or 3,3,3-trifluoropropyl.
 15. The method of claim 12wherein, M¹ is zirconium, R¹ and R² are identical and are methyl orchlorine, R³ and R^(3′) are identical and are each methyl, n-heptyl,n-octyl, n-nonyl, n-decyl, cyclohexyl-methyl, t-butyl-methyl,(1-adamantyl)methyl, (2-adamantyl)methyl, benzyl, phenethyl orphenyl-propyl, R⁴ and R^(4′) are identical and are each a hydrogen atom,R⁵, R^(5′), R⁸ and R^(8′) are identical and are each phenyl, 1-naphthyl,2-naphtyl, 4-methyl-phenyl, 4-ethyl-phenyl, 4-i-propyl-phenyl,44-butyl-phenyl, 3,5-dimethylphenyl, 3,5-di-t-butyl-4-methoxy-phenyl,2,3,4,5,6-pentafluorophenyl, R⁶, R^(6′), R⁷ and R^(7′) are identical andare each a hydrogen atom the bridging unit R¹⁰ is R⁴⁰R⁴¹Si═ orR⁴⁰R⁴¹Ge═, where R⁴⁰ and R⁴¹ are identical or different and are methyl,ethyl, propyl, butyl; pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, cyclopentyl, cyclopentadienyl, cyclohexyl, phenyl,naphthyl, benzyl, or 3,3,3-trifluoropropyl.
 16. The method of claim 12wherein the catalyst system further including an aluminoxane, a Lewisacid or an ionic compound capable of converting the metallocene compoundto a cationic compound.
 17. The method of claim 16 wherein thealuminoxane is a compound having the general formula selected from oneof formulas 6, 7, 8, or 9:

wherein radicals R in the formulas (6), (7), (8) and (9) can beidentical or different and are each a an alkyl group of from 1 to about6 carbon atoms, an aryl group of from 6 to about 18 carbon atoms, benzylor hydrogen and p is an integer from 2 to
 50. 18. The catalystcomposition of claim 16 wherein the Lewis acid is a compound havingformula 10:M²X¹X²X³  (Formula 10) where M² is B, Al or Ga, and X¹, X² and X³ arethe same or different and each are a hydrogen atom, an alkyl group offrom 1 to about 20 carbon atoms, an aryl group of from 6 to about 15carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each havingfrom 1 to 10 carbon atoms in the alkyl radical and from 6-20 carbonatoms in the aryl radical or fluorine, chlorine, bromine or iodine. 19.The method of claim 18 wherein the Lewis acid comprises one or morecompounds selected from the group consisting of trimethylaluminum,triethylaluminum, triisobutylaluminum, tributylaluminum,trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane,tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane,tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane,tris(tolyl)borane, tris(3,S-dimethyl-phenyl)borane,tris(3,5-difluorophenyl)borane and tris(3,4,S-trifluorophenyl)borane.20. The method of claim 16 wherein the ionic compound comprises one ormore compound selected from the group consisting of:triethylammoniumtetra(phenyl)borate,tributylammoniumtetra(phenyl)borate,trimethylammoniumtetra(tolyl)borate, tributylammoniumtetra(tolyl)borate,tributylammoniumtetra(pentafluorophenyl)borate,tributylammoniurntetra(pentaffluorophenyl) aluminate,tripropylammoniumtetra(dimethylphenyl)borate,tributylammoniumtetra(trifluoromethylphenyl)borate,tributylammoniumtetra(4-fluorophenyl)borate,N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borateN,N-dimethylaniliniumtetra(phenyl)borate,N,N-diethylaniliniumtetra(phenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,di(propyl)ammoniurntetrakis(pentafluorophenyl)borate,di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate,triphenylphosphoniumtetrakis(phenyl)borate,triethylphosphoniumtetrakis(phenyl)borate,diphenylphosphoniumtetrakis(phenyl)borate,tri(methylphenyl)phosphoniuintetrakis(phenyl)borate,tri(dimethylphenyl)phosphoninmtetrakis(phenyl)borate,triphenylcarbeniumtetrakis(pentafluorophenyl)borate,triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,triphenylcarbeniumtetrakis(phenyl)aluminate,ferroceniumtetrakis(pentailuorophenyl)borate andferroceniumtetrakis(pentafluorophenyl)aluminate.
 21. The method of claim12 wherein the one or more olefins include propylene and/or ethylene.22. The method of claim 21 wherein the one or more olefins furtherinclude one or more of 1-butene, hexene, 1,4-butadiene, norbornadiene,ethylidenenorbornene of ethylnorbornadiene.
 23. A method for preparing abridged metallocene comprising: a) providing a compound having theformula 1a

b) reacting the compound of formula 1a with a base under reactionconditions sufficient to achieve deprotonation of the compound havingformula 1 a; c) reacting the deprotonated compound of step (b) with acompound having the formula M¹²R⁴⁰R⁴¹X₂ wherein M¹² is silicon,germanium or tin, R⁴⁰ and R⁴¹, even when bearing the same index, can beidentical or different and are each a hydrogen atom, or a hydrocarbongroup which may optionally be halogenated or which may contain heteroatoms selected from Si, B, Al, O, S, N and P, wherein the hydrocarbongroup is selected from an alkyl group having from 1 to about 30 carbonatoms, an aryl group of from 6 to about 40 carbon atoms, a fluoroalkylgroup of from 1 to about 10 carbon atoms, an alkoxy group of from 1 toabout 10 carbon atoms, an aryloxy group of from 6 to about 10 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, an arylalkylgroup of from 7 to about 40 carbon atoms, an alkylaryl group of from 7to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl,alkyl(aryl)silyl group, an arylsilyl group and an arylalkenyl group offrom 8 to about 40 carbon atoms, or wherein R⁴⁰ and R⁴¹ together withthe atoms connecting them can form one or more cyclic systems, and X isa halogen or another leaving group like triflate, tosylate, or mesylate,to provide a compound having formula 1b

wherein R³ and R^(3′) are identical or different and are each a halogenatom, or a linear, cyclic or branched hydrocarbon group which mayoptionally be halogenated and/or may contain one or more hetero atomsselected from Si, B, Al, O, S, N and P, said hydrocarbon group beingselected from an alkyl group of from 1 to about 20 carbon atoms, analkylalkenyl group of from 3 to about 20 carbon atoms, an alkylarylgroup of from 7 to about 40 carbon atoms, an alkylarylalkenyl group offrom 9 to about 40 carbon atoms, an arylalkyl group of 7 to 20 carbonatoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl groupof from 6 to about 20 carbon atoms, heteroaryl group of 3 to about 20carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, asilyloxy group of about 3 to 20 carbon atoms, an alkenyl group of from 2to about 10 carbon atoms and a NR₂ ³² group, where R³² is an alkyl groupof from 1 to about 10 carbon atoms or an aryl group of from 6 to about14 carbon atoms, R⁴ and R^(4′) are identical or different and are each ahydrogen atom, a halogen atom, or a linear, cyclic or branchedhydrocarbon group which may be halogenated and/or may contain one ormore hetero atoms selected from Si, B, Al, O, S, N and P, saidhydrocarbon group being selected from an alkyl group of from 1 to about20 carbon atoms, an alkylalkenyl group of from 3 to about 20 carbonatoms, an alkylaryl group of from 7 to about 40 carbon atoms, analkylarylalkenyl group of from 9 to about 40 carbon atoms, an arylalkylgroup of 7 to 20 carbon atoms, an alkoxy group of from 1 to about 10carbon atoms, an aryl group of from 6 to about 20 carbon atoms, aheteroaryl group of 3 to about 20 carbon atoms, an aryloxy group of from6 to about 10 carbon atoms, a silyloxy group of about 3 to 20 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, a halogenatom and a NR₂ group, where R is an alkyl group of from 1 to about 10carbon atoms or an aryl group of from 6 to about 14 carbon atoms, R⁵,R^(5′), R⁸ and R^(8′) are identical or different and are each an arylgroup of from 6 to about 40 carbon atoms, an alkylaryl group of from 7to about 40 carbon atoms, an alkenylaryl group of from 8 to about 40carbon atoms, a substituted or unsubstituted silylaryl group, or an(alkyl)(silyl)aryl group, and optionally may be halogenated and/or maycontain one or more hetero atoms selected from Si, B, Al, O, S, N and P,R⁶, R^(6′), R⁷ and R^(7′) are identical or different and are each ahydrogen atom, a halogen, or a linear, cyclic or branched hydrocarbongroup which may optionally be halogenated and/or may contain one or morehetero atoms selected from Si, B, Al, O, S, N and P, wherein thehydrocarbon group is selected from an alkyl group of from 1 to about 20carbon atoms, an alkylalkenyl group of from 3 to about 20 carbon atoms,an alkylaryl group of from 7 to about 40 carbon atoms, analkylarylalkenyl group of from 9 to about 40 carbon atoms, an arylalkylgroup of 7 to 20 carbon atoms, an alkoxy group of from 1 to about 10carbon atoms, an aryl group of from 6 to about 20 carbon atoms, aheteroaryl group of 3 to about 20 carbon atoms, an aryloxy group of from6 to about 10 carbon atoms, a silyloxy group of about 3 to 20 carbonatoms, an alkenyl group of from 2 to about 10 carbon atoms, a halogenatom and a NR₂ ³² group, where R³² is an alkyl group of from 1 to about10 carbon atoms or an aryl group of from 6 to about 0.14 carbon atoms,R¹⁰ is a bridging group wherein R¹⁰ is selected from:

where R⁴⁰ and R⁴¹, even when bearing the same index, can be identical ordifferent and are each a hydrogen atom, or a hydrocarbon group which mayoptionally be halogenated or which may contain hetero atoms selectedfrom Si, B, Al, O, S, N and P, wherein the hydrocarbon group is selectedfrom an alkyl group having from 1 to about 30 carbon atoms, an arylgroup of from 6 to about 40 carbon atoms, a fluoroalkyl group of from 1to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbonatoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenylgroup of from 2 to about 10 carbon atoms, an arylalkyl group of from 7to about 40 carbon atoms, an alkylaryl group of from 7 to about 40carbon atoms, a substituted or unsubstituted alkylsilyl,alkyl(aryl)silyl group, an arylsilyl group and an arylalkenyl group offrom 8 to about 40 carbon atoms, or wherein R⁴⁰ and R⁴¹ together withthe atoms connecting them can form one or more cyclic systems, x is aninteger from 1 to 18, M¹² is silicon, germanium or tin, and R¹⁰ may alsolink two units of the formula 1 to one another; d) reacting the compoundof formula 1b with a base under conditions sufficient to achieve doubledeprotonation of the compound of formula 1b; and e) reacting the doubledeprotonated compound from step (d) with a compound having the formulaM¹Cl₄ wherein M¹ is zirconium, titanium or hafnium, to provide a bridgedmetallocene compound of substantially 100% pure racemic isomer assynthesized.
 24. The method of claim 23 wherein the base is n-butyllithium.
 25. The method of claim 23 wherein the steps (b) and (d) ofdeprotonation are carried out at a temperature of from about −70° C. toabout 80° C.
 26. The method of claim 23 wherein M¹² is silicon and M¹ iszirconium.
 27. The catalyst composition of claim 1, wherein themetallocene compound having formula 1 is selected from the groupconsisting ofDimethylsilanediylbis(2-methyl-4,7-diphenyl-indenyl)zirconiumdichloride; Dimethylsilanediylbis(2-ethyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-propyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-i-propyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-butyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-s-butyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-pentyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-hexyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-heptyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-methyl-4,7-diphenyl-indenyl)zirconiumdichloride, Dimethylsilanediylbis(2,4,7-triphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-benzyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenethyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylpropyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylbutyl-4,7-diphenyl-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-methyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-ethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-propyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-i-propyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-butyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-s-butyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-benzyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenethyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(4-methyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-methyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-ethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-propyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-i-propyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-butyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-s-butyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-benzyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenethyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(4-t-butyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-methyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-ethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-propyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-i-propyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-butyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-s-butyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-benzyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenethyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(3,5-dimethyl-phenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-methyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-ethyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-propyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-i-propyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-butyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-s-butyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-ftiryl)-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-benzyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenethyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylbutyl-4,7-bis-(1-naphthyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-methyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-ethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-propyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-i-propyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-butyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-s-butyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-pentyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-hexyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-n-heptyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopropylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclobutylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclopentylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cyclohexylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-cycloheptylmethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-adamantyl)methyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-t-butyl-methyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-(1-furyl)-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-benzyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenethyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride,Dimethylsilanediylbis(2-phenylpropyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride andDimethylsilanediylbis(2-phenylbutyl-4,7-bis-(9-anthracenyl)-indenyl)zirconiumdichloride.